SOLUTIONS OF EXERCISES

LEVEL 0

001 equilibrium

001:1 vessels with water in thermal contact

It is plausible to assume that the heat involved in changing the temperature of a
quantity of water by one degree is proportional to its mass and more or less constant
between the given temperatures, say C units per kg, so that
10.(te − 50)·C + 5.(te − 25)·C = 0.
Equilibrium temperature te = 41 ⅔ °C

001:2 vessels with water in thermal contact

The equilibrium temperature (46.4 °C) differs considerably from 41 ⅔ °C (foregoing
exc). Apparently the property C is different for different substances.
10 ·(te − 50) · CH2O + 5 ·(te − 25 ) · CH2 SO4 = 0
CH2 SO4 = 0.34 CH2O

001:3 sulphuric acid poured into water

The heat of mixing (of two different substances) comes into action; the final
temperature is not the same.

002 variables

002:1 the air’s pressure at the Puy de Dôme

725 Torr and 639 Torr, respectively.

002:2 pressure at top and bottom

101329 Pa.

002:3 Fahrenheit’s temperature scale

t' t 9
= × + 32 −17.8 °C 35.6 °C
°F °C 5

002:4 two phases and their amounts of two substances

added together in phase LI in phase LII

n(A) n(C) n(A) n(C) n(A) n(C)
10 10 6 2 4 8
5 5 3 1 2 4
6 4 4.8 1.6 1.2 2.4
2 8 0 0 2 8
320 Solutions

002:5 ethanol and water saturate a space

P = (300/760) · 101325 Pa
P·V
V = 50·10-3 m3 n= = 0.722 mol
RT
T = 333.15 K
ethanol mole fraction in vapour - in equilibrium with liquid at 60 °C and 300 Torr - is
about 0.57.
amount of ethanol = 0.57 · 0.722 mol = 0.41 mol
amount of water = 0.43 · 0.722 mol = 0.31 mol

003 the rules of the game

003:1 three variables subjected to two conditions

There is one independent variable, because of M − N = 3 − 2 = 1. Taking X as the
independent variable, then

{ Y (X) = − 2 X
Z (X) = X

003:2 phase diagram or not?

The phase diagram is supposed to be the graphical representation of the mole
fractions of pairs of coexisting phases as a function of T (or P). Hence, for every point
of the vaporus there has to be a corresponding point on the liquidus. In the case of
figure a) this obvious rule is violated. In the case of b) the rule is respected; however,
for thermodynamic reasons, as will be seen later on, the two curves are allowed to
make contact in an extremum only.

a) b)

003:3 derivation of lever rule

from “law of conservation of substance B”
i.e. overall amount of B = amount of B in α + amount of B in β
Xo {n(α) + n(β)} = Xα · n(α) + Xβ · n(β)

003:4 a system formulation

In addition to the three liquid phases I, II and III there, obviously, is a vapour phase V
M = M ⎡⎣P, X BI , XCI , X BII , XCII , X BIII , XCIII , X BV , XCV ⎤⎦

N = N ⎡⎣ μ AI = μ AII = μ AIII = μVA , μBI = μBII = μBIII = μBV , μCI = μCII = μCIII = μCV ⎤⎦

f=M−N=9–9=0
Solutions 321

003:5 amounts of three phases out of three substances

n(α) = 0.846 mol ; n(β) = 1.538 mol ; n(γ) = 0.615 mol

003:6 the experimental advantage of a small vapour phase

In liquid + vapour equilibrium experiments with low vapour pressures and carried out
such that the vapour phase occupies but a small fraction of the space, the equilibrium
composition of the liquid phase is ‘forced’ to be equal to the overall composition, Xo
(before the experiment adjusted by the investigator), within experimental uncertainty.
As an (extreme) example, if Xo = 0.0500 and Xvap = 0.99 and n(liq) = 105 n(vap), then
Xliq = (calculated value) 0.0499906.
As a result: the answer is Xliq = 0.20 and P = 287.7

003:7 naphthalene is added little by little to toluene

0.25 0.5
X

0.25 0.5
o
X
003:8 does an empty place matter?
Each new open place makes that the number of variables will be one less, just like
the number of conditions; in the end f remains equal to c − p + 2.

004 pure substances

004:1 the position of phase symbols

fields: β top; γ right; α bottom left
increasing entropy: α, β, γ
322 Solutions

004:2 zero Celsius and zero Celsius

T ·ΔV
ΔT = = ΔP
Q
apply SI units
273 K·( − 1.63 · 10-6 m3 ·mol−1 )
= (611 − 101325) Pa
6008J·mol−1
= 0.0075 K the answer is 7 mK

004:3 water’s triple point pressure

A priori:
the data indicate that the result will be close to 0 °C
and (4.579/760)·101325 Pa = 610.5 Pa
Calculations:
• lin. least sq. of pairs {y = ln (P sol /P liq); x = (273.15 + t) -1}
for y = 0, calculate x → 273.15 + t /°C = 273.159
• lin. least sq. of pairs { y = ln (P sol ); x = (273.15 + t) -1}
for x = (273.159)-1, calculate y → P = 4.5822 Torr
or P liq data → P = 4.5822 Torr
result:
t = 0.01 °C; P = 4.5822 Torr = 610.9 Pa; rounded: 611 Pa.

004:4 carbon dioxide’s metastable normal boiling point

Qliq → vap ≈ 17 kJ·mol-1
Tnbp ≈ 185 K

004:5 the substance water under high pressure

liquid → solid at 100°C: at about 2.5 GPa
triple point (II + V + l): in vicinity of (−19 °C; 0.32 GPa)
see also (Fletcher 1970)

004:6 a rule to be respected by metastable extensions

→ for spontaneous change the shaded field is
• at the α side of (α + β): β → α ⎫ ⎫
⎬γ→α ⎪
• at the β side of (β + γ) : γ → β ⎭ ⎬⊗
⎪
• at the γ side of (α + γ): α→γ⎭
⊗ this is the absurdity!

004:7 a phase diagram acts as a thermobarometer

800
• Triple point at 620 ºC and
I 0.55GPa
• Equilibrium (I+III):
600
II
dt/dP = 530 K·GPa-1.
t/°C
• Rules for equilibrium
III lines (metastable
400
extensions)
• III at high-pressure side

0 P/GPa 1
Solutions 323

004:8 superposition of stable and metastable

P
L

(β) α

T
004:9 Antoine’s equation
A = 15.7576 B = 2408.66 C = 62.060
with these values the following pressures, expressed in Torr, are calculated
289.15 433.56 759.94 1267.95 2025.98
the mean absolute difference in experimental and calculated pressure is just 0.03
Torr (and partly due to round-off effects)!

004:10 supercritical fluid

L
S

P V

004:11 iron: the heat effect of magnetic change

rounded to an integer in kJ·mol-1: 8; heat needed 35.6 kJ

004:12 boiling water altimeter

Combine d(lnP)/dT (from the Clapeyron equation) with d(lnP)/dh (from the
barometric formula ←002); heat of vaporization 41kJ.mol-1.

005 binary and ternary systems

005:1 a unary diagram made to look like a binary one

triple point → eutectic type of three-phase equilibrium
boiling curve → two-phase region like region of demixing in Figure 3
324 Solutions

005:2 the amounts of the phases during an experiment

n(α) n(β) n(L)
i = 0 0
ii < 0 >
iii < > >
iv 0 < >
v 0 0 =

005:3 phase diagram and cooling curve

temp. (interval) phase(s) change in temp. is
600 to 515 °C liq fast
515 to ~ 350 °C liq + sol (LiCl) slow
at 350 °C liq + sol (LiCl) + sol (KCl) zero
350 to 200 °C sol (LiCl) + sol (KCl) fast

005:4 a reciprocal system

Two variables:
X (the fraction of the cations that are K+)
Y (the fraction of the anions that are Br-)
a composition square, of which the vertexes are occupied by the pure substances:
NaCl (X= 0; Y = 0 ); KCl (1; 0); KBr (1; 1); NaBr (0; 1)

005:5 increasing repulsive interaction and the phase diagram

The change to liquid is more and more “postponed” to higher temperatures: the A
liquidus (except for its initial part) is moving upwards, and the eutectic point is moving
up to B’s melting point. From a certain “moment” on the A liquidus will be interrupted
by a (liquid + liquid) region of demixing - together involving a monetectic three-phase
equilibrium.

005:6 overlapping two-phase regions

The two three-phase equilibrium temperatures are given by the intersections of the
(β + L) solidus and the upper solvus of the (α + β) field. The (α + L) field is between
the two three-phase equilibrium lines; and such that the (metastable parts of) the
(β + L) liquidus and the (α + β) lower solvus are inside the field.

005:7 the construction of ternary phase diagrams

R = racemate = compound AB; Q = quasiracemate = compound AC
section stable solids single-phase fields two-phase fields invariant triangles
i) C L C+L
R R+L
ii) *) (A) L (A + L)
(B) (B + L)
C C+L CLQ
Q Q+L
R R+L
iii) A 2 times L A+L ALR
B B+L BLR
Solutions 325

C C+L CLR
Q Q+L CQR
R R+L LQR
• temperature is just above or just below m.p. of A and B

005:8 the appearance of an incongruently melting compound

The sequences of the (two -) and single-phase fields are, when considered from high
to low temperature and from left to right (assuming that B’s melting point is below the
peritectic temperature):
L
(A + L) L
(A + AB) (AB + L) L
(A + AB) (AB + L) L (L + B)
(A + AB) (AB + B)

005:9 ternary compositions having a constant ratio of the mole fractions of two
components
AR : XB for Q; SB: XA for Q
AP : XB for P; PB; XA for P
Ratios: AP : PB = RP : PS
= (AP − RP) : (PB − PS)
= AR : SB QED

005:10 cyclohexane with aniline - mixing and demixing

Temperature 19.5 ºC - the milky aspect of tube 1.
Initial slopes (negligence of solid-state solubility), given as dT/dX: at cyclohexane (C)
side 245 K; at aniline (A) side 56 K.
The phase diagram, from low to high temperature:
at −11 ºC three-phase equilibrium solid C + liquid (X = 0.93) + solid A;
at −2 ºC three-phase equilibrium (lower boundary of region of demixing) solid (C) +
liquid (X = 0.035) + liquid (X =0.88);
critical point (top of region of demixing) at 31.2 ºC (Xc = 0.43);
the liquid+vapour two-phase region is bent downwards (repulsive aspect of
interaction between C and A), but does not give rise to a minimum.

006 distribution and separation

006:1 a room saturated with water

From P·V = n·R·T it follows n = 255.53 mol;
This amount corresponds to 4.603 kg;
The increase is 5.6% per degree.

006:2 solubility of potassium permanganate in boiling water

Just as an observation,
by linear regression of lnm as a function of (t + 273.15)-1, the solubility at 100 °C is
calculated as 3.92 mol·kg-1.
326 Solutions

006:3 the space needed to remove an impurity

V ≥ 196 dm3

006:4 extraction and clever use of solvent

One time with 1 kg : 0.010 mol of S remain in water;
two times with 0.5 kg: 0.0056 mol of S remain in water.

006:5 distillation with a fractionating column

In terms of mole fraction, and Xaz for the azeotropic composition.

a b c d e
first drop X=0 X=0 X = 0.5 X = Xaz X=0
residue X=1 X=1 X = 0.5 X=1 X = Xaz

006:6 single-step distillation of wine

In spite of the need of liquidus data for X > 0.9, the answer seems to be “yes”.

100

90

80

006:7 vacuum distillation

⎛P ⎞ ΔH ⎛ 1 1 ⎞
ln ⎜ 2 ⎟ = − ⎜ − ⎟
⎝ P1 ⎠ R ⎝ T2 T1 ⎠
T1 = n.b.p; P2 = 15 Torr; P1 = 760 Torr ( = 1 atm); ΔH = 11·R·T1
p-xylene T2 /K = 303
2–nitro–p–xylene 379
4–methylbenzaldehyde 352.

006:8 distillation with steam

TX diagram: it has the type of Figure 005:4.
• The distillate, with overall composition X = 0.045,
contains 21.22 mol of water
• water layer 21.13 mol; aniline layer 1.09 mol
• 21.13 mol of LI contains 0.148 mol of aniline:
15% of the yield!
Solutions 327

006:9 a congruently crystallizing compound

H 2O

r
b

A A 3B B

• Overall composition: a→b→c→d

b→c: B crystallizes
c→d: A3B and B crystallize together;
mother liquor: a→b→r
• 2 mol A0.75B : 1 mol B; or, 0.5 mol A3B : 1 mol B
NB It makes no difference whether or not the solid material is continuously removed
(see next exc).

006:10 an incongruently crystallizing hydrate

H 2O

b
r
g
c

A B
328 Solutions

• Mother liquor a→b→r→g

b → r: B crystallizes
r → g: H crystallizes
at g H crystallizes together with A
• Solid material not removed: for overall composition from c to H, solid B
reacts with the invariant solution (r) to produce the hydrate H.

006:11 recrystallization
i) 2 g of impurity
• to dissolve 98 g KClO3: 0.1744 kg of water needed;
• remains in solution at 0°C: 5.77 g of KClO3;
yield = (98 − 5.77) g = 92.23 g; 94%
ii) 10 g of impurity
• to prevent any recrystallization of KMnO4: 0.3544 kg of water needed;
• remains in solution at 0°C:11.70 g of KClO3
yield = (90 − 11.70) g = 73.30 g; (87%)
NB. It is tacitly assumed that the two salts do not influence each others solubility
in a given amount of water (→ Exc 13)
See also (Mulder and Verdonk 1984).

006:12 a saturation problem

A and C become saturated at the same time (!),
as a result, after the addition of 1.2 g of C:
solid phase B 0.2 g
liquid phase A contains 0.8 g of B
liquid phase C contains 0.2 g of B
saturation of A with B : μBA = μBsol (1)
distribution of B over A and C: :μ = μ
A
B
C
B (2)
from (1) and (2): :μ = μ
C
B
sol
B (3)
(3): saturation of C with B

006:13 back to the analogy – the text around figures 1 and 2

• Let, in the triangle ABC, point a on the side AC and point b on the side BC
represent the saturated solutions. Then, the whole phase diagram is defined
by the straight lines Ab and Ba.
• The solubility curves in the rectangular YX diagram have the same course as
the vaporus curves in the PX diagram; that is to say, if the latter, in contrast
to Figure 006:2, is not plotted upside down.
At three-phase equilibrium the liquid phase has X = 0.273; Y = 0.478.

007 chemical equilibrium

007:1 the exerted pressure

P = 14 decabar.
Solutions 329

007:2 the equilibrium constant of the ammonia equilibrium

Extrapolated value 6.50·10-3 atm-1 = 6.42·10-3 bar-1
NB The square of this value corresponds to the K defined by Equations (9) and (10).
The value of the ΔGo property becomes ΔGo (T = 723.15 K) = 61 kJ·mol-1; Po = 1 bar.

007:3 Clausius-Clapeyron plot of Horstmann’s data

About 175 kJ·mol-1

007:4 the equipment to be used

• vessel-with-manometer, because there is only one degree of freedom:

1 (1 − α ) 0.5α 1.5α
X HCl = ; X NH3 = ; X N2 = ; X H2 =
(2 + α ) (2 + α ) (2 + α ) (2 + α )

f = M[T , P,α ] − N ⎡⎣ μNH4Cl = μNH3 + μNHCl ; μNH3 = 0.5 μN2 + 1.5 μH2 ⎤⎦ = 3 − 2 = 1

007:5 three pure substances taking part in a reaction

Pure substances: there are no composition variables.
f = M[T , P ] − N [ μ A + μB = μC ] = 2 − 1 = 1 :
only one of the variables T and P can be chosen in an arbitrary manner.
The answer is NO!

007:6 Professor Denbigh’s example from the zinc smelting industry

Three phases
f = M ⎡⎣T , P, X Zn
vap vap
⎤ − N ⎡ μZn
vap
+ μCO
vap
= μZnO + μC ; μZn
vap
+ μCO
vap vap ⎤
= μZnO + μCO
, XCO ⎦ ⎣ 2 ⎦=2
“c” = f + p − 2 = 3; Zn , CO, CO2
Four phases
f = M[ same] − N ⎡⎣same plus μZn
liq
= μZn
vap
⎤ = 4−3 =1
⎦
“c” = 3; Zn , CO, CO2
see also (Denbigh 1955)
 LEVEL 1

101 differential expressions

101:1 the ideal gas

RT ⎛ ∂P ⎞ R ⎛ ∂P ⎞ RT
P= ⎜ ∂T ⎟ = V ⎜ ∂V ⎟ = − 2
V ⎝ ⎠V ⎝ ⎠T V

2
∂P
2
∂P RT ∂ 2P R ∂ 2P
=0 =2 3 =− 2 =
∂T 2 ∂V 2 V ∂V ∂T V ∂T ∂V

PV ⎛ ∂T ⎞ V ⎛ ∂T ⎞ P
T = ⎜ ∂P ⎟ = R ⎜ ∂V ⎟ = R
R ⎝ ⎠V ⎝ ⎠P

∂ 2T ∂ 2T ∂ 2T 1 ∂ 2T
=0 =0 = =
∂P 2 ∂V 2 ∂V ∂P R ∂P ∂V

101:2 the Van der Waals gas

RT a
P (V,T ) = −
(V − b ) V2

⎛ ∂P ⎞ ⎛ ∂P ⎞ ⎧ RT 2a ⎫ ⎛ R ⎞
dP = ⎜ ⎟ dV + ⎜ ∂T ⎟ dT = ⎨− + 3 ⎬ dV + ⎜ ⎟ dT
⎝ ∂V ⎠T ⎝ ⎠V ⎩ (V − b )2
V ⎭ ⎝ (V − b ) ⎠

101:3 integration of different expressions along different routes

expression route change

(A) (1) 71

(A) (2) 71

(B) (1) 25

(B) (2) 39

(A), the calculated change of which is independent of the route followed,

corresponds to the total differential of a function Z of X and Y:
Z(X,Y) = X2 Y3 + constant
(B) is not the total differential of a function Z of X and Y.
Solutions 331

101:4 a simplistic method

R(T + dT ) R(T + dT )
V (T + dT , P + dP ) = =
( P + dP ) ⎛ dP ⎞
P ⎜1+
⎝ P ⎟⎠

R(T + dT ) ⎛ dP ⎞ RT R RT
= ⎜ 1 − P ⎟ = P + P dT − 2 dP − .....dTdP
P ⎝ ⎠ P

RT
dV = V (T + dT,P + dP ) − V (P,T ) = R dT − 2 dP
P P

102 work heat energy

102:1 q and the cross-differentiation identity

⎛ ∂U ⎞ ⎡⎛ ∂U ⎞ ⎤
q=⎜ ⎟ dT + ⎢⎜ ∂V ⎟ + P ⎥ dV
⎝ ∂T ⎠V ⎣⎝ ⎠T ⎦
This form does not obey the cross-differentiation identy
2
∂ U
2
∂ U ⎛ ∂P ⎞
≠ + ⎜ ⎟
∂V ∂T ∂T ∂V ⎝ ∂T ⎠V
as (∂P/∂T)V is not equal to zero.

102:2 units and conversion

1 J = 1 N·m (newton x meter)
= 1 kg·m·s –2·m = 1 kg·m2·s -2
1 Pa = 1 N·m-2 = 1 J·m-3
1 m3 = 1 J·Pa-1
1 cm3·atm = 10-6 m3 x 101325 Pa = 0.101325 J

102:3 reaction between zinc and sulphuric acid

P P = 1 atm

RT
ΔV =
P

ΔW = −∫PdV at isobaric conditions = − P ∫dV = −PΔV = −RT

−RT = −8.3145 J·K-1·mol -1 x 298.15 K = −2479 J·mol -1
−PΔV = − 1 atm ⋅ RT/P x 103 = −24.47 atm x dm3·mol-1 = −24.47 liter x atm·mol-1
332 Solutions

The work added to the system per mole generated hydrogen is −2479 J = 24.47
liter x atm

103 heat capacity and enthalpy

103:1 a classroom calorimeter

heat added 750 J·s-1 x 120 s = 90000 J
rise in temperature 9.05 K
heat capacity 90000 J / 9.05 K = 9.94 kJ·K-1

103:2 a drop calorimeter

the effect is 64.80 x 333.5 = 21.61kJ per 100 g
which is 13.73 kJ·mol-1; therefore
(HT − H273) for T = 800 K is 13.7 kJ·mol -1
the mean specific heat capacity of copper is 0.410 J·K-1·g -1.

103:3 a cycle passed by a monatomic gas

P /atm V /dm3 T /K

A 1 24.45 298

B 1 48.91 596

C 2 24.45 596

change nature qrev /J wrev /J ΔU /J ΔH /J

1 isobaric 6194 −2478 3717 6194

2 isothermal −3435 3435 0 0

3 isochoric −3717 0 −3717 −6194

cycle −957 957 0 0

103:4 heat at constant pressure

qrev = dU + PdV qrev = dH − VdP
dH = dU + PdV +VdP and (qrev)P = dH
By the way, in the text it was first discovered that at constant P the heat added to
the system corresponds to the change of (U +PV) which was subsequently defined
as H; in this exercise first H is defined.... to descover that at constant P...

103:5 choice of zero point

U = H − PV ⇒ U = −PV
oxygen gas U = −RT = − 2479 J·mol -1
diamond U = −1 Pa x 3.417x10-6 m-3·mol-1 = −3.4 x 10-6 J·mol -1
Solutions 333

103:6 heat added to silver bromide

T = 313.71 K.
50.763 J·K-1·mol-1
Robie et al. (1978) give 50.734 obtained with heat of melting of 9.163 kJ·mol -1 and
the given CP formula.

103:7 an interpolation formula for CP for diamond

30

20

CP 0.2 kJ·mol
-1

-1 -1
J·K ·mol x ~ 150 ≈ 30 kJ·mol
-1

0
400 800 1200 1600
T/K

-1
31.42kJ·mol

104 the ideal gas – expansion and compression

104:1 a simulation of isothermal compression

• From pV = nRT, n = 0.040 mol
• ΔW = nRTln2 = 69.3 J = −ΔQ
• ΔT = −ΔQ / (heat capacity) = 2 mK

104:2 adiabatic compression

• qrev = 0 ; Wrev = −PdV = − (RT / V) dV
d U = (C + CVgas )d T
dU = Wrev ;(C + C Vgas )dT/T = −R (dV/V )
(C + CVgas ) ln(T2 /T1 ) = −Rln(V2 /V1 )
for C = 0 T2 = 872 K
• for C = 500 J ⋅ K-1 T2 = 306 K

104:3 adiabatic compression of helium

• ΔS = CP ln (T2 / T1) − R ln (P2 / P1), which in this case = 0. State B: T = 749 K
334 Solutions

800
B
T/K

500

A
200
0 5 10 P/bar

104:4 expansion of a Van der waals gas

V =V 2 V2 dV ⎛ 1 1⎞
( ΔU )T = ∫V =V 1
(∂U / ∂V )T dV = a ∫
V1 V
2
= a⎜− + ⎟
⎝ V 2 V1 ⎠
with V2 = 2V1 , (ΔU)T = a /(2V1) (ΔU)T = 70 J ⋅ mol-1
70 J are taken: the temperature of the whole set-up is lowered by 0.005 K

104:5 volume quotients for a cycle

Adiabatic dU = Wrev, which for the ideal gas gives rise to

⎛ RT ⎞ dT dV
CV dT = − ⎜ ⎟ dV ; CV = −R ; CV d lnT = − RdlnV
⎝ V ⎠ T V
⎛T ⎞ ⎛V ⎞ ⎛V ⎞ ⎛V ⎞
CV ln ⎜ 2 ⎟ = − R ln ⎜ 2 ⎟ = R ln ⎜ D ⎟ = − R ln ⎜ C ⎟
⎜T ⎟ ⎜V ⎟ ⎜V ⎟ ⎜V ⎟
⎝ 1⎠ ⎝ 1⎠ ⎝ A⎠ ⎝ B⎠

so that V D = V C or V B = V C
VA VB VA VD

104:6 an equation for an adiabatic

• Ideal gas: dU = CV dT; CP = CV + R
adiabatic: dU = Wrev = −P dV
taking P and V as the two independent variables, dT for the ideal gas can
be given as dT = (V/R) dP + (P/R) dV; the adiabatic now satisfies the
equation
CV (V/R) dP + CV (P/R) dV = − PdV, from which it follows
(CV / R) (dP / P) = − (CP / R) (dV / V), or d lnP / d lnV = −CP /CV Equation (1)
upon integration it follows from Equation (1): P ·V Cp / Cv = constant
• for each point in the PV plane d lnP/d lnV has one single value: through the
point there goes just one adiabatic; or, in other words, adiabatics do not
intersect.
Solutions 335

104:7 ideal gas, expansivity and compressibility

1 ⎛ ∂V ⎞ 1 1 ⎛ ∂V ⎞ 1
α= ⎜ ⎟ ideal gas α = κ =− ⎜ ⎟ ideal gas κ =
V ⎝ ∂T ⎠ P T V ⎝ ∂P ⎠T P
⎛ ∂V ⎞ ⎛ ∂V ⎞
dV = ⎜
∂ T ⎟ dT + ⎜ ∂P ⎟ dP = αVdT − κVdP or d lnV = α dT − κ dP
⎝ ⎠P ⎝ ⎠T
⎛ ∂α ⎞ ⎛ ∂κ ⎞
cross-differentiation identity: ⎜ ∂P ⎟ = −⎜ ∂T ⎟
⎝ ⎠T ⎝ ⎠P
ideal gas 0 = 0

104:8 isothermal compression of Van der Waals gas

1 ⎛ ∂V ⎞ ⎛ ∂P ⎞
κ =− ⎜ κ −1 = −V ⎜
V ⎝ ∂P ⎟⎠T ⎟
⎝ ∂V ⎠T
1
ideal gas κ ID = ; ( 1 − α ) -1 for α → 0 is 1 + α
P
For the van der Waals gas, substitution (∂P / ∂V)T, see Exc 4.

−1 RTV 2a RT V 2a RT ⎛ b ⎞ 2a
κVDW = − = · − = · 1+ −
(V − b )2 V
2
(V − b ) (V − b ) V 2 (V − b ) ⎝⎜ V ⎠⎟ V 2

RT a RT b a
= − + · −
(V − b) V 2 (V − b ) V V 2

⎛ b⎞ a ⎛ b a ⎞
≈ P ⎜1 + ⎟ − 2 = P ⎜1 + − 2 ⎟
⎝ V⎠ V ⎝ V PV ⎠
1⎛ b a ⎞
κVDW = ⎜ 1 − +
P ⎝ V PV 2 ⎟⎠
b a
correction term =− +
V P V2

105 chemical energy

105:1 formation of liquid water

• Strictly speaking, if one specifies the PT circumstances for the enthalpy
effect, one should also specify P and T for the energy effect;
• the difference between the two effects is ΔRH − ΔRU = P·ΔRV, where
Δ RV = VH2O − VH2 − 1/ 2 VO2 ;
-1
PVH2 and PVO2 are about equal to RT which is 2479 J·mol at 298.15 K;
-1
PVH2O is about just 2 J·mol ;
as a result, the difference P·ΔRV is about - 1 (1/2)RT and rounded to kJ it is
−4.

105:2 formation of gaseous water

• −243 kJ·mol-1
• for liquid H2O we have at 1 atm (1 bar)
3
Δ f HH2O = −284x10 at T = 373.15 K
-3
Δ f HH2O = −286x10 at T = 298.15 K
336 Solutions

Δ f C P H 2O ≈ 2x10 3 / 75 ≈ 3x10 J ·K -1·mol −1

by the way,
Δ f CP H2O = CPH2O − CPH2 − 1/ 2 CPO2

105:3 reaction between graphite and carbon dioxide

• At constant P, ΔQ = ΔH = 172.8 kJ·mol--1;
• the work performed by the system equals + PΔV, ΔV = 2VCO − VCO2 − VC ,
which is, in the ideal-gas approximation for CO and CO2 and using the given
density of graphite, 2RT/P − RT/P − 5.3x10-6 m3·mol-1.
+ PΔV = 2479 − 0.5(!) = 2478 J·mol-1
• ΔU = (heat taken by the system) – (work done by the system)
= 172.8 − 2.5 = 170.3 kJ·mol-1
(the influence of the volume of graphite is really negligible)

105:4 enthalpy of formation

Taking ethanol (C2H6O), the following two possibilities present themselves - with E for
ethanol

o
a) Δf H400 = HE (P = 1 unit , T = 400 K) − 2 HC (P = 1;T = 400) − 3 HH2 (P = 1;T = 400)
− 0.5 HO2 (P = 1; T = 400)

b) o
Δ f H400 = HE (P = 1, T = 400) ∑ − 2 HC (P = 1;T = 298) − 3 HH2 (P = 1;T = 298)
− 0.5 HO2 (P = 1; T = 298)
The information needed, starting from Δ f H298
o
,

b) for E: CP liquid from 298.15 K to boiling point at unit pressure (b.p); heat of
vaporization at b.p; CP gas from b.p. to 400 K
a) in addition: the CP ‘s of graphite, hydrogen and oxygen.

105:5 reaction between hydrogen and chlorine

In an isolated system the energy is constant: the chemical energy released by the
reaction is stored in the vessel with its contents - rise in temperature, say from Tb to
Te. The easiest way to show that there is, under these conditions, no "conservation of
enthalpy" is to consider the limiting case, in which the vessel has zero heat capacity
(i.e. to consider its contents only). Assuming ideal-gas behaviour and taking 1/2 n
mol H2, then we have for H2 + Cl2 → · 2HCl
Hbegin = Ubegin + nRTb
Hend = Uend + nRTe
ΔH = ΔU + nR(Te − Tb) = 0 + nR(Te − Tb) ≠ 0

105:6 formation of magnesite

Δ f HMgCO3 = − 1113.28 kJ·mol-1
Solutions 337

105:7 standard formation energies

PV ΔfUo (298.15K)
J·mol-1 kJ·mol-1

graphite 0.53 −0.001

silicon 1.21 −0.001

oxygen 2478.97 −2.479

carbon monoxide 2478.97 −111.769 ± 0.170

carbon dioxide 2478.97 −393.509 ± 0.130

quartz 2.27 −908.222 ± 1.000

o
o
CO : Δ f U CO = U CO
o
− U Co − 1/ 2 U Oo 2 = (HCO − RT ) − (HCo − PVC ) − 1/ 2(HOo2 − RT)
= 111769 J·mol-1

105:8 acetic acid from methanol and carbon monoxide

o
To start with, the heat effect at 1 atm and 298.15 K, i.e. ΔH298 , is calculated from
the heats of combustion.

CH3OH + 3/2O2 → CO2 + 2H2O −725.7

CO + 1/2O2 → CO2 −283.0
2CO2 + 2H2O → CH3COOH +874.4

CH3OH + CO → CH3COOH −134.3 kJ·mol-1

o
ΔH298 = − 134.3 kJ·mol-1

Next, for each of the three substances, the difference in Ho corresponding to the
change in temperature from 298.15 K to 500 K, has to be calculated.
methanol
vap
o o
H500 − H298 = CPo298 (Tb − 298.15K) + ΔHVo + CPT
o
b
(500K − Tb )

= 81.6 (338 − 298.15) + 35300 + 44 (500 − 338)

= 45.68 kJ·mol-1
carbon monoxide
o o
H500 - H298 = 29.1 (500 − 298.15)
= 5.87 kJ·mol-1
acetic acid
º º
H500 − H298 = 123.4 (391 − 298.15) + 44400 + 67 (500 − 391)
= 63.16 kJ·mol-1
Finally
o o
ΔH500 − H298 = 63.16 − 45.68 − 5.87 = 11.6 kJ·mol-1
o
ΔH298 = − 134.3 + 11.6 = − 122.7 kJ·mol-1
338 Solutions

105:9 combustion of benzoic acid

• C6H5COOH + 7.5O2 → 7CO2 + 3H2O; ΔH = −3227 kJ·mol-1
7CO2 → 7C + 7O2 +2755
3H2O → 3H2 + 1.5O2 +858

C6H5COOH → 7C + 3H2 + O2 +386

ΔfH = −386 kJ·mol-1

• C6H5COOH(sol) + 7.5O2 → 7CO2 + 3H2O(liq) ; ΔH = −3227 kJ·mol-1

C6H5COOH(liq) → C6H5COOH(sol) −17
3H2O(liq) → 3H2O(liq) −123

C6H5COOH(liq) +7.5O2 → 7CO2 + 3H2O(vap); ΔH = −3121 kJ·mol-1

105:10 a reaction in a bomb calorimeter

• Reaction C2H4O2 + 2O2 → 2CO2 + 2H2O
equal amounts of gaseous species at both sides:
(ΔQ)V ~ (ΔQ)P = ΔH = ΔHo in ideal-gas approximation
1.874 K x 15250 J·K-1 = 28578 J (per 1.96 g)
molair mass: 60 g·mol-1
ΔC Ho = −875 kJ·mol-1 (heat of combustion)

2 CO2 + 2 H2O → C2H4 O2 + 2 O2 + 875

2 O2 + 2 C → 2 CO2 − 787.0
2 H2 + O2 → 2 H2O − 571.7
2 H2 + 2 C + O2 → C2H4 O2 − 484
ΔfHo = −484 kJ·mol -1

106 entropy

106:1 absolute entropy by graphical integration

CP / T
-2 -1
calth·K ·mol -2
25 K x 0.0005 calth·K ·mol
-1

0.005 -1 -1
= 0.0125 cal th ·K ·mol
about 45.5 times and to be
multiplied by 4.184 yields
-1 -1
2.38J·K ·mol

0.000
0 200 T/K
See also Table 109:1a
Solutions 339

106:2 absolute entropy of liquid sodium chloride

The value given in Robie's table is 170.33 J·K-1·mol-1

106:3 gaseous mercury and the Sackur-Tetrode equation

It is clear that the entropy values have been calculated by means of the S-T
equation.
The equation implies a constant CP , having the value of 2.5 R.
(from qrev = CP dT it follows dS = (qrev /T =) (CP /T) dT and CP = T (∂S / ∂T)P)

106:4 orientations up and down

ΔS = (R/N) ln (Wb / Wa) = (R/N) ln2N = R ln 2
each possible orientation of one unit can be combined with two orientations of all
the other units.

106:5 substitutional disorder of red and blue molecules

See § 204 "the ideal mixture"

106:6 cylinder with internal piston and entropy

4.2

S
Arbitrary
units

4.0

3.8

4 6 8 10 12 position
NB If the piston can freely move, it will spontaneously move to position 8, i.e. the
position of maximal entropy. See also Figure 001:2.

106:7 uniform pressure at maximum entropy

V1 + V2 = const = V
S/R = n1 lnV1 + n2 lnV2 = lnV1n1 ·V2n2 = lnV1n1 ·(V − V1 )n2

((
condition dS/dV1 = 0, or d V1n1 ·(V − V1 )
n2
) / dV )
1 = 0

this leads to n1·V2 = n2·V1

and with V2 = n2 (RT /P2) and V1 = n1 (RT /P1)
it follows P1 = P2 !
340 Solutions

106:8 two vessels with helium in thermal contact

Along with T + |ΔT| there is a P + |ΔP| and P − |ΔP| with T − |ΔT|. From PV = RT,
(ΔP/ΔT)V = R/V = P/T and hence ΔP/P = ΔT/T.
Next
5 ⎧ T
2
⎫ ⎧ P
2
⎫
ΔS = R ln ⎨ ⎬ − R ln ⎨ ⎬
2 ⎩ (T + | ΔT |) (T − | Δ T |) ⎭ ⎩ (P + | Δ P |) (P − | Δ P |) ⎭
5 ⎛ ⎛ ΔT ⎞ 2 ⎞ ⎛ ⎛ ΔP ⎞ 2 ⎞
=− R ln ⎜ 1 − ⎜ ⎟ ⎟ + R ln ⎜ 1 − ⎜ ⎟
2 ⎜ ⎟ ⎜ ⎝ P ⎟⎠ ⎟
⎝ ⎝ T ⎠ ⎠ ⎝ ⎠
2 2 2
5 ⎛ ΔT ⎞ ⎛ ΔP ⎞ 3 ⎛ ΔT ⎞
≈ R⎜ −R ⎜ ⎟ = R⎜
2 ⎝ T ⎟⎠ ⎝ P ⎠ 2 ⎝ T ⎠
⎟

106:9 supercooled water made to crystallize

During a "reversible simulation" of the spontaneous change, first heat is added to
one mole of water to bring its temperature from −5°C to 0°C and next the same
amount of heat is withdrawn as a result of which part of the water crystallizes to ice.
• The amount of heat added is 5 x 75 = 375 J.
The entropy change is
273.15 dT 375
75 ∫ − = 1.386 − 1.373 = + 0.013 J· K -1
263.15 T 273.15
• 375 / 6000 = 1 / 16

107 characteristic functions

107:1 the Maxwell relations differently

⎛ ∂S ⎞ ⎛ ∂S ⎞
Substitute dS = ⎜ ⎟ dT + ⎜ ∂V ⎟ dV
⎝ ∂T ⎠V ⎝ ⎠T
in dU = T dS − P dV and obtain
⎛ ∂S ⎞ ⎡ ⎛ ∂S ⎞ ⎤
dU = T ⎜ ⎟ dT + ⎢T ⎜ ∂V ⎟ − P ⎥ dV
⎝ ∂T ⎠V ⎣ ⎝ ⎠T ⎦
Next apply the cross-differentiation identity to the last dU
∂ 2S ∂ 2S ⎛ ∂S ⎞ ⎛ ∂P ⎞
T =T + −
∂V ∂T ∂T ∂V ⎜⎝ ∂V ⎟⎠T ⎜⎝ ∂T ⎟⎠V
⎛ ∂S ⎞ ⎛ ∂P ⎞
Hence ⎜ ⎟ =⎜ ⎟
⎝ ∂V ⎠T ⎝ ∂T ⎠V

107:2 differential coefficients of energy

From dU = T dS − P dV it follows

⎛ ∂U ⎞ ⎛ ∂S ⎞ ⎛ ∂V ⎞
⎜ ∂P ⎟ = T ⎜ ∂P ⎟ − P ⎜ ∂P ⎟
⎝ ⎠T ⎝ ⎠T ⎝ ⎠T

⎛ ∂V ⎞ ⎛ ∂V ⎞
= −T ⎜
∂T ⎟ − P ⎜ ∂P ⎟ = −T ·α ·V + P·κ ·V
⎝ ⎠P ⎝ ⎠T
⎛ ∂U ⎞ ⎛ ∂S ⎞ ⎛ ∂V ⎞
and ⎜ ∂T ⎟ = T ⎜ ∂T ⎟ − P ⎜ ∂T ⎟ = CP − P·α ·V
⎝ ⎠P ⎝ ⎠P ⎝ ⎠P
Solutions 341

107:3 total differential of enthalpy

dH = TdS + VdP

⎧⎛ ∂S ⎞ ⎛ ∂S ⎞ ⎫
= T ⎨⎜ ⎟ dT + ⎜ ∂P ⎟ dP ⎬ + VdP
⎩⎝ ∂T ⎠P ⎝ ⎠T ⎭
⎛ ∂V ⎞
= CP dT − T ⎜ ⎟ dP + VdP
⎝ ∂T ⎠P
= CP dT − T αVdP + VdP
So, if you want to “correct” H for changes in P and T you need to know the heat
capacity; the volume; and the cubic expansion coefficient.

107:4 model system with equation of state

• dH = T dS + V dP
⎛ ∂H ⎞ ⎛ ∂S ⎞ ⎛ ∂V ⎞
⎜ ∂P ⎟ = T ⎜ ∂P ⎟ + V = −T ⎜ ∂T ⎟ + V = b
⎝ ⎠T ⎝ ⎠T ⎝ ⎠P
RT
Maxwell and V = +b
P
HT does depend on P: HT (P2) = HT (P1) + b (P2 – P1)
• dU = TdS − PdV
⎛ ∂U ⎞ ⎛ ∂S ⎞ ⎛ ∂V ⎞ ⎛ ∂V ⎞ ⎛ ∂V ⎞
⎜ ∂P ⎟ = T ⎜ ∂P ⎟ − P ⎜ ∂P ⎟ = −T ⎜ ∂T ⎟ − P ⎜ ∂P ⎟
⎝ ⎠T ⎝ ⎠T ⎝ ⎠T ⎝ ⎠P ⎝ ⎠T

R ⎛ RT ⎞
= −T − P⎜− 2 ⎟=0
P ⎝ P ⎠
At constant temperature the energy is independent of pressure.

107:5 Van der Waals gas - change of enthalpy with volume

From dH = T dS + V dP it follows
⎛ ∂H ⎞ ⎛ ∂S ⎞ ⎛ ∂P ⎞
⎜ ∂V ⎟ = T ⎜ ∂V ⎟ + V ⎜ ∂V ⎟
⎝ ⎠T ⎝ ⎠T ⎝ ⎠T
and with one of the Maxwell relations
⎛ ∂H ⎞ ⎛ ∂P ⎞ ⎛ ∂P ⎞
⎜ ∂V ⎟ = T ⎜ ∂T ⎟ + V ⎜ ∂V ⎟
⎝ ⎠T ⎝ ⎠V ⎝ ⎠T
Rearranging the VDW equation, P = RT/(V − b) − a/V 2.

⎛ ∂H ⎞
⎜ ∂V ⎟ = −RTb / (V − b ) + 2a / V
2 2

⎝ ⎠T

107:6 change of heat capacity with pressure

(
CP = −T ∂ 2G / ∂T 2)
⎛ ∂CP ⎞ ∂ 3G
⎜ ∂P ⎟ = −T = (cross - differentation identity)
⎝ ⎠T ∂P ∂T 2
∂ 3G ∂ 2V
= −T 2
= −T
∂T ∂P ∂T 2
342 Solutions

107:7 Gibbs energy of a hypothetical system

S = −β − β lnT − γ ln P − ε − ϕP;
V = γ(T / P ) + δ + ϕT ;

H = α − β T + δP; CP = −β

( ∂P ∂T )V
2
= ( γP + ϕP ) /( γT ) from Equation (107 : 25).
U = α − β T − γT − ϕPT ;

⎛ ∂U ⎞ ⎛ ∂U ⎞
dU = ⎜ ⎟ dT + ⎜ ∂P ⎟ dP;
⎝ ∂T ⎠P ⎝ ⎠T
⎛ ∂U ⎞ ⎛ ∂U ⎞ ⎛ ∂U ⎞ ⎛ ∂P ⎞ 2 2
CV = ⎜ ⎟ =⎜ ⎟ +⎜ ⎟ ⎜ ⎟ = −β − γ − 2ϕP − (ϕ / γ )P ;
⎝ ∂T ⎠V ⎝ ∂T ⎠P ⎝ ∂P ⎠T ⎝ ∂T ⎠V
under isothermal (T = Ta) conditions
P = P2 ⎛ γ ⎞
ΔQrev = Ta ∫ (dS )T = Ta ∫ − − ϕ ⎟ dP
P=P ⎜ P
1 ⎝ ⎠
P2
= −γTa ln − ϕTa (P2 − P1 )
P1

107:9 Joule-Thomson coefficient

⎛ ∂H ⎞ ⎛ ∂P ⎞ ⎛ ∂T ⎞
From ⎜ ⎟ ⎜ ⎟ ⎜ ⎟ = −1
⎝ ∂T ⎠P ⎝ ∂H ⎠T ⎝ ∂P ⎠H
⎛ ∂H ⎞ ⎛ ∂P ⎞
⎜ ∂T ⎟ = CP and ⎜ ⎟ from
⎝ ⎠P ⎝ ∂H ⎠T
⎛ ∂H ⎞ ⎛ ∂S ⎞
dH = TdS + VdP, i.e, ⎜ ⎟ = T ⎜ ∂P ⎟ + V
⎝ ∂P ⎠T ⎝ ⎠T
and one of the Maxwell relations.

107:10 difference between CP and CV

⎛ ∂U ⎞ ⎛ ∂U ⎞
From dU = ⎜ ⎟ dT + ⎜ ∂P ⎟ dP it follows
⎝ ∂T ⎠P ⎝ ⎠T
⎛ ∂U ⎞ ⎛ ∂ U ⎞ ⎛ ∂U ⎞ ⎛ ∂P ⎞
CV = ⎜ ⎟ =⎜ ⎟ +⎜ ⎟ ⎜ ⎟
⎝ ∂T ⎠V ⎝ ∂T ⎠P ⎝ ∂P ⎠T ⎝ ∂T ⎠V
⎛ ∂U ⎞ ⎛ ∂U ⎞ ⎛ ∂P ⎞
See Exc 2 for ⎜ ⎟ and ⎜ ∂P ⎟ and Equation (107:25) for ⎜ ∂T ⎟ .
⎝ ∂T ⎠P ⎝ ⎠T ⎝ ⎠V

107:11 enthalpy as a characteristic function

⎛ ∂H ⎞ ⎛ ∂H ⎞
dH = TdS + VdP ; T = ⎜ ⎟ and V = ⎜ ∂P ⎟
⎝ ∂S ⎠P ⎝ ⎠S
⎛ ∂H ⎞
• G = H − TS = H − S ⎜ ⎟
⎝ ∂S ⎠P
⎛ ∂H ⎞
• U = H − PV = H − P ⎜ ⎟
⎝ ∂P ⎠S
-1 −1
⎛ ∂H ⎞ ⎛ ∂S ⎞ ⎡⎛ ∂T ⎞ ⎤ ⎛ ∂H ⎞ ⎡ ∂ 2H ⎤
• CP = ⎜ ⎟ =T ⎜ ⎟ = T ⎢⎜ ⎟ ⎥ = ⎜ ∂S ⎟ ⎢ 2⎥
⎝ ∂T ⎠P ⎝ ∂T ⎠P ⎣⎝ ∂S ⎠P ⎦ ⎝ ⎠P ⎣ ∂S ⎦
Solutions 343

⎛ ∂U ⎞ ⎛ ∂S ⎞
• CV = ⎜ ⎟ = T ⎜ ∂T ⎟
⎝ ∂T ⎠V ⎝ ⎠V
⎛ ∂T ⎞ ⎛ ∂T ⎞
use dT = ⎜ ⎟ dS + ⎜ ∂P ⎟ dP from which
⎝ ∂S ⎠P ⎝ ⎠S

⎛ ∂T ⎞ ⎛ ∂S ⎞ ⎛ ∂T ⎞ ⎛ ∂P ⎞
1= ⎜ ⎟ ⎜ ⎟ +⎜ ⎟ ⎜ ⎟
⎝ ∂S ⎠P ⎝ ∂T ⎠V ⎝ ∂P ⎠S ⎝ ∂T ⎠V

⎛ ∂T ⎞ ⎛ ∂T ⎞ ⎛ ∂S ⎞ ⎛ ∂T ⎞
and also ⎜ ⎟ =⎜ ⎟ ⎜ ⎟ +⎜ ⎟ ;
⎝ ∂P ⎠V ⎝ ∂S ⎠P ⎝ ∂P ⎠V ⎝ ∂P ⎠S

⎛ ∂S ⎞ ⎛ ∂S ⎞ ⎛ ∂P ⎞ ⎛ ∂V ⎞
⎜ ∂P ⎟ from ⎜ ∂V ⎟ ⎜ ∂S ⎟ ⎜ ∂P ⎟ = −1
⎝ ⎠V ⎝ ⎠P ⎝ ⎠V ⎝ ⎠S

107:12 energy expressed in T and P

If U would be characteristic for T and P then it would be possible to derive V from
U(T, P);
for the ideal gas U does not depend on V:
V cannot be derived just from U(T);
Therefore
U impossibly can be characteristic for T and P

107:13 a cosmetic imperfection?

The expression in the thesis gives the dependence of a Gibbs energy property on T
and P. Mathematically speaking, taking into account that the energy property is
provided with (T,P), a more consequent expression would be
ΔG(T,P) = ΔU(T,P) + PΔV − TΔS.
If the latter is meant to state that energy is a function of T and P, and that the volume
and entropy properties are constants, then the expression is incorrect from a
thermodynamic point of view, as follows from the differential coefficients in Exc 2.

108 Gibbs energy and equilibrium

108:1 entropy versus energy diagram

dU = TdS − PdV
⎛ ∂U ⎞
⎜ ∂S ⎟ = T
⎝ ⎠V
positive slope of U versus S
i.e. positive slope of S versus U
-1
∂ 2U ⎛ ∂T ⎞ ⎛ ∂S ⎞
=⎜ ⎟ =⎜ ⎟
⎝ ∂S ⎠V ⎝ ∂T ⎠V
2
∂S
U versus S is convex (second derivative is positive)
i. e. S versus U is concave
344 Solutions

spontaneous at constant U

U spontaneous at constant S
U decreases

108:2 a fancy device

Take 1 mol water and suppose that n mol of it crystallizes. Then
ΔS = 75 ln(273.15/268.15) − n 6000 / 273.15.
Constant entropy demands that ΔS = 0.
As a result n = 0.06308.
ΔU = 5 x 75 − n·6000 = 375 − 378.5 = −3.5 J

108:3 Gibbs energy of ideal gas

⎛ ∂G ⎞ ⎛ ∂G o ⎞ o
S = −⎜ ⎟ = −⎜ ⎟ − R ln P = S (T ) − R ln P
⎝ ∂T ⎠P ⎝ ∂T ⎠P
⎛ ∂G ⎞ RT
V =⎜ ⎟ = P
⎝ ∂P ⎠T

H = G + TS = G o + TS o + RT ln P − RT ln P = H o (T )
RT
U = H − PV = H o − P = H o (T ) − RT = U o (T )
P
by the way, in Hoand Uo the superscript o has lost its meaning

108:4 ammonia’s Gibbs energy of formation

1
2N 2 + 3 2 H 2 → NH 3
for 25 °C and all gases at a certain pressure P

obar obar obar

Δ f GNH3 = GNH 3
+ RT ln(P / bar) − 3 2 GH2 − 3 2 RT ln(P /bar) − 1
2 GN2 − 2 RT
1 ln(P / bar)
obar
= Δf G − RT ln(P / bar)
= −16410 − RT ln(P /105Pa)
= − 16410 + RT ln 105 − RT ln (P / Pa)
= − 16410 + 28540 − RT ln (P / Pa)
oPa
Δ f GNH 3
= + 12.13 kJ · mol-1

108:5 an equation of state for real gases

On integration from 1 Pa at constant temperature
G(P) = G(P =1Pa) + RT lnP + B(P − 1Pa);
on generalization, and neglecting Bx1Pa,
G(T,P) = Go(T) + RT lnP + B(T) P
H(T,P) = Ho(T) + B(T) − T (dB/dT)
Solutions 345

108:6 the concept of fugacity

f(T,P) = P·e B(T )·P / RT
for N2 at 673 K and 101325 Pa f = 101369 Pa

108:7 water + ice under a higher pressure

The two lines have to be lifted up; the line for ice, with its greater molar volume,
more than the line for water: the point of intersection is at a lower temperature.

108:8 the calcium carbonate equilibrium under a higher pressure

With GB* (T = T ) = GB* (T = To ) − SB* (T − To )
B = CO 2, CaO, CaCO 3

ln P =
*
GCaCO3
*
(To ) − GCaO *
(To ) − GCO2
( *
(To ) − SCaCO3
*
− SCaO o
− SCO2
)
(T − To )
RT

* * *
GCaCO3
(To ) − GCaO (To ) − GCO2
(To ) = 0 for To = 1160 K

* * o
SCaCO3
− SCaO − SCO2
= −144 J · mol-1
for P = 1.25 bar T = 1175 K

108:9 the calcite and aragonite forms of calcium carbonate

Calcite at 1160 K
CAL
GCaCO3
− GCaO − GCO2 = 0
aragonite at 1160 K, as a result of GARA > GCAL,

ARA
GCaCO3
− GCaO − GCO2 > 0
ARA
GCaCO3
> GCaO + GCO2
aragonite has already passed the equilibrium curve: it changes spontaneously into
CaO and CO2
Conclusion: aragonite decomposes at a lower temperature

108:10 liquid and gaseous water in equilibrium

• 373.15 K; 1 atm.
ΔG = ΔH − T ΔS = 0 so that ΔS = 109.52 J·K-1·mol-1
ΔU = ΔH − P ΔV ≈ ΔH − P Vvap ≈ ΔH − R T = 37763 J·mol-1
• 372.15 K; 1 atm.
ΔG = ΔH − T ΔS = 110 J·mol-1
• 374.15 K; 1 atm.
ΔG = −110 J·mol-1

108:11 lowest Helmholtz energy as a criterion for equilibrium

Starting from Equation (6), and replacing Equation (8) by A = U − TS, the criterion
expressed by Equation (11) becomes (dA)T,V ≤ 0.
346 Solutions

109 data and tables

109:1 partial derivatives of H-TS

⎛ ∂f ⎞ ⎛ ∂H ⎞ ⎛ ∂S ⎞
⎜ ∂T ⎟ = ⎜ ∂T ⎟ − T ⎜ ∂T ⎟ − S
⎝ ⎠P ⎝ ⎠P ⎝ ⎠P
= CP − CP − S = −S
⎛ ∂f ⎞ ⎛ ∂H ⎞ ⎛ ∂S ⎞
⎜ ∂P ⎟ = ⎜ ∂P ⎟ − T ⎜ ∂P ⎟
⎝ ⎠T ⎝ ⎠T ⎝ ⎠T
⎧ ⎛ ∂S ⎞ ⎫ ⎛ ∂S ⎞
= ⎨T ⎜ ⎟ + V ⎬ − T ⎜ ∂P ⎟ = V
⎩ ⎝ ∂P ⎠T ⎭ ⎝ ⎠T

109:2 completion of a table

5.74 0 0 0

33.15 0 0 0

205.15 0 0 0

197.67 −110.53 89.36 −137.17

213.79 −393.51 2.92 −394.38

42.62 −157.32 −93.11 −129.56

109:3 the essential information of a table

The information needed is:
the entropy of each of the five substances;
for the compounds the heat of formation:
for MgO and SiO2 from the elements;
for Mg2SiO4 either from the elements or from the oxides.

109:4 thermodynamic table for corundum

• Δ f H o = −1675.700 kJ· mol-1 ΔfSo= −313.505 J·K-1·mol-1
Δ f G o = −1582.228 kJ·mol-1

• with the above values and Δ f CPo = −13.665 J·K-1·mol-1

Δ f H o = −1677.092 kJ·mol-1 ⎪⎫
⎬ Δ f G o = −1550.084 kJ·mol-1
Δ f S o = −317.521 J·K -1·mol-1 ⎪⎭

109:5 thermodynamic table for helium from the Sackur-Tetrode equation

⎛ ∂S ⎞
CP, from CP = T ⎜ 5
⎟ , is constant and equal to 2 R.
⎝ ∂T ⎠P
(HTo − H298
o
) /T = 14.589 J·K-1·mol-1
Solutions 347

STo = 151.308 J·K-1·mol-1

−(GTo − H298
o
) /T = 136.72 J·K-1·mol-1

109:6 extrapolation formula for Gibbs energy

∫θ (CP ) ∫θ (CP )
T T T
HT − Hθ = θ
+ C' ∫ dT dT = θ
+ C' (T − θ ) dT
θ

= CPθ (T − θ ) + C' ⎡
⎣ ( 1
2 )
T 2 − 21 θ 2 − θ (T − θ )⎤
⎦

T (C Pθ
T
+ ∫ C'dT
θ ) dT
ST − Sθ = ∫θ T
⎛T ⎞ ⎡ ⎛T ⎞ ⎤
= CPθ ln ⎜ ⎟ + C' ⎢(T − θ ) ) − θ ln ⎜ θ ⎟ ⎥
⎝θ ⎠ ⎣ ⎝ ⎠⎦
GT = HT − T ST

109:7 silver oxide

by least squares: a = 49.397 J·K-1·mol-1; b = 5.5841 x 10-2 J·K-2·mol-1

T/K (H o
T − H298 ) STo

calc Table calc Table

400 7.016 7.042 141.502 141.570

500 14.469 14.509 158.108 158.212

109:8 water versus steam

(HTo − H298
o
)T STo −(GTo − H298
o
)T CPo ΔfHo ΔfGo
1) 1) 1)
298.15 water 0.000 0) 69.95 = 69.95 75.19 −285.830 −237.1411)

steam 0.000 0) 183.83 = 183.83 33.58 −241.814 −228.569

1800 water 59.236 3) 259.37 2) 200.13 3) 49.68 2) −251.2012) −147.0352)

steam 34.783 259.37 224.59 49.68 −251.201 −147.035

0)
the selected zero points;
1)
independent of choice of zero point, but different owing to difference in state, i.e.
liquid versus gaseous;
2)
independent of choice of zero point and equal, in view of equality of state;
3)
different values owing to difference in zero point.

109:9 α-quartz - molar volume and compressibility

Molar volume 31 N Av · Vunit cell = 22.7 x 10 - 6 m3 · mol -1
isothermal compressibility 1.8 x 10-11 Pa-1
348 Solutions

109:10 α-quartz - Gibbs energy at high pressure

ΔG = V ΔP ∼ V P for high pressure and starting from low pressure
= 113.5 kJ·mol-1
from V = Vo(1 − κ·P)
ΔG = Vo·P (1 − ½ κ·P) = 108.4 kJ·mol-1
4 ½ % lower

109:11 the change in Gibbs energy resulting from a change in pressure

P
G (P ) − G(π ) = ∫π V (P )dP
P⎛ P⎛ ∂V ⎞ ⎞
= ∫π ⎜⎝Vπ + ∫π ⎜⎝ ∂P ⎟⎠T dP ⎟⎠ dP
etc.
= V (π )·(P − π ) + 21 V' (π )(P − π )2 + 61 V'' (π )(P − π )3

this result is just a Taylor’s series

109:12 bulk modulus

⎛ ∂P ⎞
Taking MB as MB = −V ⎜ ⎟ , i. e. isothermal bulk modulus, we obtain
⎝ ∂V ⎠T
κ = MB-1
⎛ ∂V ⎞ V
⎜ ∂P ⎟ = − M
⎝ ⎠T B

⎛ ∂ 2V ⎞ V ⎡ ⎛ ∂MB ⎞ ⎤
⎜ 2 ⎟ = 2 ⎢1 + ⎜ ⎟ ⎥
⎝ ∂P ⎠T T MB ⎣ ⎝ ∂P ⎠T ⎦

109:13 forsterite at high pressure

V (π )·(P − π ) = 235.8 kJ·mol−1
1
2
V' (π )(P − π )2 = −6.70
1
6
V'' (π )(P − π )3 = 0.13

P < Ptr P = Ptr P > Ptr

v v v
l l l
s
G* s G* G* s

s s s
l
l l

v v v

T
α = sol; β = liq; γ = vap
Solutions 349

110 pure substances

110:1 G*T diagrams around a triple point

see bottom foregoing page

110:2 benzophenon, a monotropic substance

G*

β
α
liq

20 40 60 t / °C
just a simple calculation:
G liq − Gα = 16700 − 52.000 T
G liq − G β = 13800 − 46.200 T
G β − Gα = 2900 − 5.88 T
= 0 for T = 493 K

110:3 a phase diagram analogue

α
Y

ε
0
0 X 6
350 Solutions

110:4 a negative degree of freedom?

α
Y

γ
δ

0
0 X 6

110:5 Antoine equation for 1-aminopropane

At n.b.p. P = 760 Torr, so that T = 320 K
d ln P B ΔH
= = (Clapeyron)
dT (T − C)2 RT 2
B·RT 2
ΔH = = 30.81 kJ·mol-1
(T − C)2

110:6 heat of melting along the melting line

dH = T dS + V dP
⎧⎛ ∂S ⎞ ⎛ ∂S ⎞ ⎫
= T ⎨⎜ ⎟ dT + ⎜ ∂P ⎟ dP ⎬ + V dP
⎩⎝ ∂T ⎠P ⎝ ⎠T ⎭
⎛ ∂V ⎞
= CP dT − T ⎜ ⎟ d P + V dP
⎝ ∂T ⎠P

dΔH dT ⎛ ∂ΔV ⎞
= ΔCP − T⎜ ⎟ + ΔV
dP dP ⎝ ∂T ⎠P

with Clayperon

ΔCP ·ΔV ⎛ ∂ΔV ⎞

=T −T ⎜ ⎟ + ΔV
ΔH ⎝ ∂T ⎠P
Solutions 351

110:7 vapour pressure over 1,4-dibromobenzene

Ho So Go
temperature 25 °C
(kJ·mol-1) (J·K ·mol-1)
-1
(kJ·mol-1)
standard pressure 1 Pa 74.00 458.57 −62.72

standard pressure 1 atm 74.00 362.73 −34.15

NB the values shown are of limited significance as CP influences and the

dependence of G*sol on pressure could not be taken into account

110:8 monoclinic and orthorhombic sulphur

HSO2 − HO2 − HSo = −296810
HSO2 − HO2 − HS m = −297210
•
ΔH = HS m − HSo = 400J·mol−1
ΔG = ΔH − T ΔS = 75 J·mol-1
• From ΔG = ΔH − T ΔS = 0 it follows T = 367 K.
• It follows that o has the lowest Gibbs energy at 25 °C. In other words,
formation properties of sulphur compounds refer to elementary sulphur in
the orthorhombic form.
The answer is −296.81 kJ · mol-1

110:9 caesium chloride

by subtraction: Δαβ G ≡ G β − Gα = −2900 + 3.91 T

transition α → liq β → liq α→β

temperature (K) 913 887** 742

heat effects (kJ·mol-1) 20.116 23.016 −2900*

*
minus sign: α is the high-, and β the low-temperature form
**
metastable melting point
stability order: β (742 K) α (913 K) liquid

110:10 diamond out of graphite

The equilibrium pressure (Pe) at 1700 K follows from
ΔG (1700 K, Pe) = ΔG (1700 K, 1 bar) + ΔV (Pe − 1 bar) = 0.
Pe = 4.8·109 Pa
Let’s say, order of magnitude needed, at least 1010 Pa. By the way, the value of Pe
for 1700 K, given by Whittaker (1978) is 6·109 Pa.
352 Solutions

110:11 heat capacity change from the shape of the arc

Taylor: F = Fo + (X−Xo) (dF /dX) + ½(X−Xo)2(d2F /dX 2) + etc.
For F = lnf
F − Fo = -h; at the top dF /dX = 0; (X−Xo) = ½ b; d2F/dX2 = (ΔCP /R) (Tmax)2

110:12 the water arc

Read from the arc, Tmax = 297.6 K; h = 0.00605; b = 0.000338 K-1.
With these numbers, Equation (30) gives ΔCP = −39.8 J.K-1.mol-1

110:13 a different arc

See Exc 11; this time the second derivative of lnf is given by [2 βT + (ΔCp/R)]/T 2
Read from the arc, Θ = 297.85 K; h = 0.0512; b = 30 K.
With these numbers, ΔCP = −39.7 J.K-1.mol-1.

110:14 naphthalene: the assessment of a data set

Among the data for vapour pressures over solids, the set of given data are of a
superior quality (see van der Linde et al. 1998); yet the construction of the arc leaves
some space for a subjective interpretation.
For two extreme arcs (having h = 0.065; b = 0.00075 K-1; and the other h = 0.040;
b = 0.00100 K-1) the calculated properties are (SI units):
ΔGo ΔHo ΔCPo T (P = 800 Pa)
h = 0.065 −6019 72500 −86.5 350.76
h = 0.040 −5957 72500 −30.0 349.90

110:15 second-order transition according to Ehrenfest

From d(ΔS*) = 0, the relationship dP/dT = (ΔCP/T)/(∂ΔV*/∂T)P ;
From d(ΔV*) = 0, the relationship dP/dT = − (∂ΔV*/∂T)P/(∂ΔV*/∂P)T

111 chemical reactions and equilibrium

111:1 the strontium oxides

• lowest G for SrO2
• with 1 mol O2: either 2 mol SrO or 1 mol SrO2;
lowest G for 2 mol of SrO
• now SrO has a lower G then SrO2;
with 1 mol O2: 1 mol SrO and ½ mol O2

111:2 Alexander von Humboldt’s discovery

• at equilibrium ΔG = ΔG o + RT ln P is equal to zero;
ΔH o = 154 kJ · mol-1
ΔS o = 139 J · K -1 · mol-1
• From Equation (007:7):
ΔG = ΔG o + RT ln( XO2 ·P ) = ΔH o − T ΔS o + RT ln( XO2 ·P )
= 154000 − 139 T + RT ln0.2
Solutions 353

ΔG is zero for T = 1014 K: up to 1014 K BaO will absorb O2 from the air.

111:3 magnesium carbonate

• straight line, passing zero at about 682 K;
• during the whole experiment the gas in the cylinder is pure CO2 at 1 bar :
isothermal decomposition at ~ 682 K.

682 K
h/cm 2 mol gas

80

1 mol gas
40

0
0 400 800 T/K

111:4 air as a CO2 buffer

Δ fox H o = − 115.4 kJ · mol-1
Δ fox S o = − 169.2 J · K -1 · mol-1
for the reaction MgCO3 → MgO + CO2 the ΔG is given by (use Equation (007:7))
ΔG = −Δ foxGMo gCO3 + RT ln ( XCO2 · P )
the asked temp is the one for which ΔG passes zero; the answer is 488 K

111:5 the ammonia equilibrium - the role of pressure

• extrapolated value 6.50·10-3 atm-1 = 6.42·10-3 bar-1
• o
RT ln K = − GNH{3
− 21 GNo2 − 32 GHo 2 } o
= − Δf GNH 3
o
result Δ f GNH 3
(723.15 K) = 30.35 kJ · mol-1
• data 700: Δ f S o = − 114 J · K -1· mol-1
• taking, for the extrapolation to 723.15 K, Δ f H o and Δ f S o constant, then
Δ f G o = 29.76 kJ · mol-1

111:6 ammonia’s degree of dissociation

In ideal gas mixture for substance B, Equation (007:7),
μB = GBo + RT ln ( X B · P )
X NH3 = (1 − α ) (1 + α ); X N2 = ( 12 α ) (1 + α ); X H2 = ( 3 2 α ) (1 + α )
⎧⎪ 3α 2 3 ⎫⎪ o
RT ln ⎨ ·P ⎬ = Δ f GNH3
⎩⎪ 4 (1 − α )
2
⎭⎪
354 Solutions

1
⎧ Δf Go RT ⎫ 2
⎪ e ⎪
α = ⎨ ⎬
Δf G o RT
⎩⎪ e + (0.75 3 ) · P ⎭⎪

P /bar →
1 10 100

0.032 0.010 0.003

0.336 0.112 0.036

0.841 0.441 0.154

0.974 0.805 0.394

111:7 vapour in equilibrium with solid salammoniac

There are two equations (equilibrium conditions) to find P and α
dissociation of salammoniac
⎧⎪ (1 − α ) 12 ⎫⎪
ln P + ln ⎨ ⎬ = −1.07393
⎩⎪ (2 + α ) ⎭⎪
dissociation of ammonia
⎧⎪ ( 1 α ) 12 · (3 α )3 2 ⎫⎪
ln P + ln ⎨ 2 2
⎬ = 3.17537
⎩⎪
(1 − α ) (2 + α ) ⎭⎪
solution α = 0.936; P = 3.96 bar;
mole fractions in the vapour phase:
HCl (0.341) NH3 (0.022) N2 (0.159) H2 (0.478)

111:8 dissociation of water at 1800 K

H2O H2 + 1/2 O2
relative amounts 1− α α 1/2 α
mole fractions (1 − α ) α 1/2 α
(1 + 1/2α ) (1 + 1/2α ) (1 + 1/2α )

⎧⎪ α ( 1 α ) 12 ⎫⎪
1
2
RT ln P + RT ln ⎨ 2
1 ⎬
= Δ f GHo 2O
⎩⎪ (1 − α ) (1 + 2 α ) ⎭⎪
1 2

this equation most easily can be solved numerically; solution: α = 0.0023

111:9 the simple model - interdependent reactions

C dependent reactions
6

B+C A+C 2B (B ) A+2D→C

4 2A+ 3 D
(D ) A+C→2B
A
2 A+D B
B D
B+D C

0 X
-2 0 2 4
Solutions 355

111:10 virtual experiments related to Figure 3

CD DA AB BC

A+B A+B C C 1/2 A + 1/2 D

A+ C 2A+B A+C A+C 3/2 A + 1/2 D
A+D 2A+2B 2C 2C A+D
B+C A+2B B+C D D
B+D A+3B 2B+C B+D B+D
C+D 2A+3B B+2C C+D C+D

111:11 one of Professor Schuiling’s favourites

( A ) Al2Si2O5(OH)4 + 2 SiO2 → Al2Si4O10(OH)2 + H2O

( Q ) Al2Si4O10(OH)2 + 2 Al2SiO5 + 5 H2O → 3 Al2Si2O5(OH)4
( W ) 2 Al2Si4O10(OH)2 → Al2Si2O5(OH)4 + Al2SiO5 + 5 Si2O

A A
Q Q

K P K A P
P K W
Q W Q
W A P K K
W
AQ
P w
AQK
P
w AQK w
P
W
AQ
K K W
Q
A K A
P P P
K P
W
Q W

Q
A
 LEVEL2

201 mixtures and partial quantities

201:1 partial volumes from densities

Referred to the same amount = 1 mol of water in each of the two mixtures:
wt % alc nalc /mol mass /g V /cm3
72 1.00621 64.2857 74.1387
73 1.05797 66.6666 77.0980

Δnalc = 0.05176 mol ΔV = 2.9593 cm3

⎛ ΔV ⎞ 3 -1
Valc ≈ ⎜ ⎟ = 57.17 cm · mol
⎝ Δnalc ⎠nw

201:2 from integral volume to partial volumes

nB2
VA = VA* + C
( nA + nB )
2

nA2
VB = VB* + C
( nA + nB )
2

201:3 zeroth degree homogeneous functions

⎛ ∂VA ⎞ ⎛ ∂VB ⎞
From dV = VA dnA + VB dnB it follows ⎜ ⎟=⎜ ⎟ (a)
⎝ ∂nB ⎠ ⎝ ∂nA ⎠
⎛ ∂V ⎞ ⎛ ∂VB ⎞
From nA dVA + nB dVB = 0 it follows nA ⎜ A ⎟ + nB ⎜ ⎟ = 0 (b)
⎝ ∂nA ⎠ ⎝ ∂nA ⎠
Substitute (a) in (b) and there you are!

201:5 molality(m) makes it easy

⎛ ∂V ⎞ dV
VB = ⎜ ⎟ which in this case is simply realizing that, in the definition of
∂n
⎝ B ⎠T,P,nH2O d m

the system, the amount of water is constant

VB = (a + 2 b·m + 3 c·m 2 ) · mol-1
Next, VH2O follows from V = nB · VB + nH2O · VH2O
VH2O = 18.015 x 10-3 ·(V o − b · m 2 − 2 c · m3 ) · mol-1

201:6 partial volumes of sodium chloride and water in their liquid mixture

VNaCl VH2O
m
cm3 · mol-1 cm3 · mol-1

0 17.4 18.05

3.0 21.6 17.94

6.01 23.0 17.84

Solutions 357

202 the open system, chemical potentials

202:1 the ammonia equilibrium from different angles

NH3 = ½ N2 + 3
2 H2

nB 1−α ½α 3
2 α

1− α 1α
2
3
2 α
XB
1+ α 1+ α 1+ α

μB = GBo + RT ln( X B ·P )
G = ∑ B nB ·μB , which gives rise to (P being 1 bar)
• (a)
= (1 − α )Δ f GNH
o
3
+ 1 o
2 GN2 + 3 2 GHo 2O + RT {(1 − α )ln(1 − α ) + 1
2 α ln( 12 α ) + 3 2 α ln( 3 2 α )
− (1 + α )ln(1 + α )}

where GNo2 and GHo 2 are arbitrary constants, which in the following are given the
value zero.

• (b)
∑ Bν B ·μB = 12 μN o + 3 2 μH
2 2
− μNH3
= −Δ f GNH3 + RT { 12 ln( 12 α ) + 3 2 ln( 3 2 α ) − ln(1 − α ) − ln(1 + α )}

NB function (b) is obtained when (a) is differentiated with respect to α.

G

All mixtures of (1 − α) mole of NH3, ½ α

mole of N2 and 3 2 α mole of H2 can be
schematically ΣBνB μB
prepared from 1 mole of NH3. Therefore,
α is identical with the “classical” degree
of dissociation. Its equilibrium value
corresponds to the minimum in the plot
of G versus α. For T = 400 K and P = 1 0
0 α 1
bar this values is 0.33.

202:2 the electrochemical cell

ΔfSo = −163.30 J.K-1.mol-1
ΔfGo = −285830 + 163.30 (T /K)
E(taken positive) = 1.23 V
At increasing temperature the Gibbs energy change becomes less negative; the
temperature coefficient, related to the entropy change, is −0.00085 V.K-1.
At increasing pressure the Gibbs energies of the reactants increase substantially
more than the Gibbs energy of the product: the Gibbs energy change becomes more
negative and, as a result, the emf increases.
The reversible heat is the product of temperature and entropy change
= −48689 J.mol-1; heat is given off.
358 Solutions

202:3 the influence of gravity

From the cross-differentiation identity, the change is given by the change of M.g with
nB , the amount of B. This is MB.g, where MB is B’s molar mass.
The function recipe is μB = GBo + RT ln P + MB ·g·h
From one layer to the other:
dμB = RT ·d(ln P) + MB ·g·h = 0;
with pressure P at altitude h, and pressure Po at h = 0, upon integration and after
rearranging the expression, Equation (002:7) is obtained.
NB:
In atmospheric reality, not only the pressure of the air, but also its composition
changes with altitude, and not to forget temperature.
A better reflection of the atmosphere is a two-component system, for which the
gravitational term has to be added to Equation (5)
Neglecting the role of temperature, you could calculate the change in altitude as a
result of which the percentage of oxygen in a mixture with nitrogen falls from 20% to
19%. Realize that there are two conditions with terms in dP, dX and dh; you can
solve the two ‘unknowns’ dX/dh and dP/dh.

203 change to molar quantities. Molar Gibbs energy

203:1 integral molar quantities are zeroth degree homogeneous functions

Make use of the properties
Z
(A) Zm = and
nA + nB
nA Z A + nB ZB
(B) Zm =
nA + nB
∂Zm ∂Z
nA + nB m when applied to (A) gives
∂nA ∂nB
⎪⎧ 1 ∂Z Z ⎪⎫ ⎪⎧ 1 ∂Z Z ⎪⎫
= nA ⎨ − 2⎬
+ nB ⎨ − 2⎬
n
⎩⎪ A + nB ∂n A ( n A + nB ) ⎭⎪ n
⎩⎪ A + nB ∂nB ( n A + nB ) ⎭⎪
nA ·Z A + nB ·ZB Z
= − = (B) − (A) = Zm − Zm = 0
nA + nB nA + nB

203:2 recipes for partial quantities in a ternary system

(dZ)T,P = ZA dnA + ZB dnB + ZC dnC (I)
Z = nA · ZA + nB · ZB + nC · ZC (II)
change into (dZm)T,P = (ZB − ZA) dX + (ZC − ZA) dY (I’)
Zm = (1 − X − Y) ZA + X ZB + Y ZC (II’)
∂Zm
from (I’): = ZB − Z A (III')
∂X
∂Zm
= ZC − Z A (IV')
∂Y
ZA, ZB and ZC can be solved from (II’), (III’) and (IV’).
Solutions 359

203:3 a Gibbs-Duhem exercise

∂Z ∂Z
Gibbs-Duhem: (1 − X ) A + X B = 0;
∂X ∂X
∂Z A
from given ZA ( X ) : = −20 X ;
∂X
∂ZB
so that = 20 (1 − X )
∂X
X=X
∂ZB
and ZB ( X ) = ZB ( X = 0) + ∫ ∂X
dX
X =0

=0 + 20 X − 10 X 2 ;
Zm = (1 − X ) Z A + X ZB = 8 − 8 X + 10 X 2 .

203:4 water + methanol: volumes, integral and partial

A B
H 2O CH3 OH

-1.33

-1.0

ΔmVm -0.70
3 -1
cm ·mol

0.0
0 X 1
for X = 0.591:
VA = 18.047 − 1.33 = 16.72 cm3·mol-1
VB = 40.46 − 0.70 = 39.76
check: 0.409 × 16.72 + 0.591 × 39.76 = 30.34
in agreement with the value given in the table

203:5 the ideal mixture

G = − 4808 J

204 the ideal mixture

204:1 a Gibbs-Duhem exercise

Yes it is:
from μ A = GA* + RT ln X A = G*A + RT ln(1 − X )
it follows - Gibbs-Duhem - that
360 Solutions

⎛ ∂μB ⎞ RT
⎜ ∂X ⎟ = X
⎝ ⎠T,P
so that (T P constant)
X=X RT
μB ( X = X ) = μB ( X = 1) + ∫ dX = GB* + R T ln X
X =1 X

204:2 mathematical analysis of a function

⎛ X ⎞
f ' = ln ⎜ ⎟
⎝ 1− X ⎠
1 1 1
f'' = + =
X 1 − X X (1 − X )

205 non ideal behaviour. Excess functions

205:1 ideal or not?

Not necessarily: GE is composed of HE and SE; (in GE = HE − T·SE) HE and T·SE
may compensate each other;
in a really ideal mixture all excess properties are zero

205:2 Gibbs-Duhem and activity

μ A = μ Ast·st·A + RT ln aA
μB = μBst·st·B + RT ln aB
daA X · aA
=−
daB (1 − X ) · aB
aA increases when aB decreases and vice versa no matter the choice of standard
states

205:3 NaCl’s activity in saturated solution

Saturated solution corresponds to
μNaCl
liq
= μNaCl
sol
;
substitution of μ - recipes:
* sol liq * sol
GNaCl + RT ln a NaCl = GNaCl ;
liq
as a result a NaCl =1 .

205:4 equality of activities

Equilibrium between phases α and β containing B; condition μBα = μBβ ;
function recipes in terms of activities in terms of activities:
μBα = μBst·st + RT ln aBα
μBβ = μBst·st + RT ln aBβ ;
it follows aBα = aBβ .
NB this is what is done with fugacities; see Prausnitz et al., 1986.
Solutions 361

205:5 heat of mixing and activity coefficients

The molar Gibbs energy of mixing {(1 − X) A + X B} is given by
Δ mG = RT {(1 − X ) ln fA (1 − X ) + X ln fB X }
The reaction for ΔmH follows from the general property
⎧ ∂(G/T) ⎫ H
⎨ ⎬ =− 2
⎩ ∂T ⎭P,X T

205:6 a convenient formula

A HE
S = X (1 − X ) [1 + B(1 − 2 X )] =
E
Θ Θ
CPE = 0
⎛ T⎞ 2
μ1E = A ⎜ 1 − ⎟ X [1 + B(3 − 4 X )] = RT ln f1
⎝ Θ⎠
⎛ T⎞
μ2E = A ⎜ 1 − ⎟ (1 − X )2 [1 + B (1 − 4 X )] = RT ln f2
⎝ Θ⎠

205:7 alcohol is mixed with water - a classroom experiment

The cylinder contains 2.85 mol of water and 0.835 mol of alcohol, the mole fraction of
the latter being 0.23.
The enthalpy effect, the heat of mixing is negative: after mixing the system gives off
heat to the surroundings, to go back to room temperature. The volume change on
mixing is also negative.
The temperature to the mixture would have if the heat of mixing were zero follows
from
2.85 x (to − 19.2) x 75.3 = 0.835 x (21.9 − to) x 111.5 → to = 20.0 oC
The heat capacity of the homogeneous mixture, assuming CPE = 0, is
(2.85 x 75.3 + 0.835 x 111.5 = 308) J.K-1.
The enthalpy effect is
− (27.3 − 20.0) x 308 J; molar excess enthalpy HE = − 0.61 kJ.mol-1.
VE = −1.1 cm3.mol-1

206 magic formulae

206:1 volume properties of supercritical carbon dioxide

V = 0.20287 dm3·mol-1
κ = 0.0275 bar-1
α = 0.0143 K-1

206:2 Van der Waals and Helmholtz

From dA = − S dT − P dV: (∂A/∂V)T = − P, which means that the curves given
correspond to the derivatives of the curves asked for, with opposite sign.
In all cases A decreases with increasing V. The PV curve for T < TC gives rise to an
AV curve with two points of inflexion.
These two points coincide for T = TC and are absent for T > TC.
362 Solutions

206:3 critical coordinates from Van der waals constants

TC, PC and VC can be solved from the three equations
RT a
(1) P= −
V − b V2
⎛ ∂P ⎞ RT 2a
(2) ⎜ ∂V ⎟ = − + =0
⎝ ⎠T (V − b )2 V 3
⎛ ∂ 2P ⎞ 2RT 6a
(3) ⎜ 2 ⎟
= 3
− 4 =0
⎝ ∂V ⎠ (V − b ) V

206:4 minimal Helmholtz energy

A Q

II

a b

VE

V
Q is the intersection of the line V = VE with the double tangent line; the lowest
possible A the system can reach is represented by Q and corresponds to
equilibrium between two phases (I) and (II) of which the molar volumes are the
abscissae of the points of contact;
Solutions 363

the amounts of the phases (I) and (II) are b / (a + b) mole and a / (a + b) mole,
respectively.

206:5 critical temperature for a model system

A·Θ
Tc =
A + 2RΘ
yes, if the condition 2RΘ < A is satisfied

206:6 spinodal and critical point for a given function

R Tspin (X) = 2 A X (1 − X) [1 + 3 B (1 − 2X)]

(9 B + 1) − 27 B 2 + 1
Xc =
18 B

207 dilute solutions

207:1 the ideal isothermal vaporus

from (PB = ) X vap ·P = X liq ·PBo Equ (17)
and (PA = ) (1 − X vap )·P = (1 − X liq )·PAo
it follows, on elimination of Xliq,
P o ·P o
P ( X vap ) = vap o A B vap o
X ·PA + (1 − X )·PB
this is a part of a rectangular hyperbola

207:2 Raoult, Henry, and Gibbs-Duhem

In the vicinity of X = 0, say for 0 < X < a with a <<1, μB is given by
R T ln X + constant.
From Gibbs-Duhem, i.e. from
∂μ ∂μ
(1 − X ) A + X B = 0 ,
∂X ∂X
∂μ
it follows (1 − X ) A + RT = 0 .
∂X
∂μ A RT RT ∂μ
So that =− =− =− A .
∂X (1 − X ) XA ∂X A
Let X 'A < (1 − a) , then
X A = X 'A RT
μ A = μ A ( X A = 1) + ∫ dX A = GA* + RT ln X A
X A =1 XA
= G*A + RT ln(1 − X )
364 Solutions

207:3 the activity coefficient

GOB

RT ln γ B

μB

m=1

207:4 the solute’s chemical potential

We know that the chemical potential of B ( μBliq ) in the “solution phase” has to be
equal to the chemical potential of B in the gas phase ( μBvap ) ; the latter is
μBvap = GBo vap + RT ln P ;
as a result μBliq = GBo vap + RT ln P ;
substitution of Henry’s Law:
μBliq = GBo vap + RT ln ( mB /κ )
= cons tan t + RT ln mB
= μBliq (m = 1) + RT ln mB
= GBo liq + RT ln mB

207:5 a strange question (?)

This is almost a trick question: the differential coefficient (∂U /∂n1) under the
conditions given is the chemical potential potential μ 1.
The difference, taking the ideal dilute solution, is − R T ΔX = - 24.8 J·mol-1

207:6 a trigonometric excess function

⎛ ∂μ AE ⎞ 2 2
⎜⎜ ⎟⎟ = an n π X sinnπX
⎝ ∂X ⎠
which is zero for X = 0

207:7 the ideal solution’s quantities

GA = μ A = GA* + RT ln(1 − X ) GB = μB = GBo + RT ln X
SA = SA* − R ln(1 − X ) SB = SBo − R ln X
H A = H *A HB = HBo
VA = VA* VB = VBo

Gm = (1 − X )GA* + XGBo + RT {(1 − X )ln(1 − X ) + X ln X }

Sm = (1 − X )SA* + XSBo − R {(1 − X )ln(1 − X ) + X ln X }
Solutions 365

Hm = (1 − X )H A* + XHBo
Vm = (1 − X )VA* + XVBo

208 the solvent laws

208:1 the solute is present in both phases

Equations of the type G*Aα = G*A β − RTX will change into G*Aα − RTY = G*A β − RTX ,
as a result of which the effect, such as ( ΔP / PAo ) will stand in relation to (X – Y)
instead of X ; and eventually may change sign (when Y > X).

208:2 chemical potentials of A in liquid and vapour versus pressure

μA
vap
T = Ta
substance A
liq In reality for straight
lines: μΑ preferably
against ln P

PA (T = Ta)
O

μA
vap μA + non-volatile
vap
subst.
T > Ta

liq
liq

P P
O
PA (T > Ta) PAO

changes with dashed lines

366 Solutions

208:3 chemical potentials of H2O in liquid and vapour versus temperature

μH 2O
liq i higher pressure:
elevation of equil. temp
vap

liq
ii addition of salt:
elevation
vap

liq
iii addition of argon:
vap lowering
Temp
100°C

208:4 the molecular formula of a hydrocarbon

2
ΔP M2
. X = = 0.00874 = ⇒ M2 = 177
Po 2
M2 + 100 78
177 g contains 167.08 g carbon → 13.9 → 14
9.91 g hydrogen → 9.9 → 10
formula C14H10
for instance anthracene

208:5 the molar mass of the solvent

ΔH *A
• X = −ΔT = 0.00868 with M1 = 78
RTAo 2
from which M2 is calculated as 178
X= = 0.01112 with M1 = 100
M2 is calculated as 178
• the answer is “yes” !
Solutions 367

208:6 initial slope of solidus

The result, indeed, is in full agreement with the calculated solidus in Figure 213:4

208:7 the intervention of a foreign gas

The liquid is put under pressure: its μA increases, because of ( ∂μ A / ∂P )T = VA .
The μA of gaseous A has to increase; this can be done by “sending” more A into the
gas phase: the partial pressure of A increases.

208:8 an equation for the relative change in partial pressure

increase in μ Aliq : VA* liq ·P ( = a)
PAo + ΔPA ΔPA
change in μ Avap : RT ln = RT ( = b)
PAo PAo
from a = b
ΔPA P
= VA* liq ·
PAo RT
RT
if Vgas is the volume of the gas phase, then V gas = n gas as a result
P
ΔPA VA* liq
= n gas
PAo V gas

209 the solute laws

209:1 the Kritchevsky-Kasarnovsky equation

• mBP : molality of B in solution in equilibrium whit gaseous B whose
pressure is P;
mBo : likewise, gaseous pressure Pº;
VBo : partial volume of B in solution phase.
• recipes of μ’s: μBvap = GBo vap + RT ln P
μBliq = GBo liq + RT ln mB + VBo (P − P o )
∼ VBo ·P for P >> Pº
substitution of recipes in equil. condition ( μBliq = μBvap ) :

under high pressure P: GBo liq + RT ln mBP + VBo ·P = GBo vap + RT ln P *)

at low pressure P o : GBo liq + RT ln mBo = GBo vap + RT ln P o
P
m P
RT ln Bo = RT ln o − VBo ·P
mB P

mBP P *) −(VBo / RT )·P

= e
mBo Po
• *) only this P can be replaced by fugacity.
368 Solutions

209:2 helium in deep ocean water

NB helium’s molar mass is unnecessarily given.
• 10 ml of ideal gas at 25 °C, 1 atm is an amount of 0.0004 mol; this amount
dissolves in 1 kg water:
o
mHe = 0.0004 mol · kg-1
• P is about 800 times Po
P −(V o / RT )·P
P
mHe o
= mHe · o e He = 0.12 mol · kg-1
P
P o
mHe ~ 300 mHe

209:3 calculation of molality and Gibbs energy

a) GB* sol = GBo + RT ln msat ⇒ msat = 0.100 mol · kg-1
X = 0.0099
b) μ Aliq = G*Aliq − RTX = −1025
μBliq = GBo + RT ln msat = −2500 ( = still GB* sol )
Gmliq = (1 − X )μ Aliq + X μBliq = −1040 J·mol-1

209:4 simultaneous saturation?

The answer is yes.
The partition of B over the two liquid phases I (mainly A) and II (mainly C) is
“controlled” by
μBI = μBII (1)
The equilibrium between solid B and (saturated) liquid I implies
μBsol = μBI (2)
From the combination of (1) and (2) it follows that I and II will be saturated at the
same time; see also Exc 006:12.

209:5 a system for storage of thermal energy

f = M [T, m ] − N ⎡⎣ μdecah. = μanh. + 10 μH2O ; μNa
sol
2 SO4
= μNa
in soln
⎤ = 2−2 = 0
2 SO4 ⎦

Make a plot of lnm versus 1/T: two straight lines can be distinguished; from the
difference between the slopes the heat effect is calculated as about 58 kJ·mol-1.The
point of intersection of the two lines is at about 32.5°C

209:6 mixing of salt and water

The source of the effect is the heat of solution. Apparently, the compiler of the table
in question did not give attention to the solubility of the salts. If the solubility is less
than 50 g per 50 g of water, it may happen that the fall in temperature with less
than 50 g of salt is greater than the figure in the table - owing to the fact that the
heat capacity of the combination is lower than in the 50/50 case.
Solutions 369

210 ideal equilibria

210:1 deviation from ideal vapour pressure

In Scheme 2 insert the excess part of A’s chemical potential in the liquid phase.
Next, with the modified chemical potential(s), repeat the route from Equation (1) to
Equation (3). The diagnostic formula is Ω = 4 R T ln (P / Pid.)

210:2 like and unlike

Methanol (A) + 1-propanol (B) Ω = 161 J·mol-1
Isobutylalcohol (A) + toluene (B) Ω = 2948 J·mol-1

210:3 entropies of vaporization from phase diagram data

Equations
{
(1 − X liq ) = (1 − X vap )exp ΔS*A (TAo − T ) / RT }
X liq
=X vap
exp { ΔSB* (TBo − T ) / RT }
mean values found ΔS*A = 9.54 R
ΔSB* = 9.80 R

210:4 point of inflexion in ideal liquidus

d2 X ⎛ ΔS*A ·TAo ⎞ 1 ⎛ ΔS*A ·TAo ⎞

2
= X ⎜⎜ ⎟⎟ 3 ⎜⎜ − 2 ⎟⎟
dT ⎝ R ⎠T ⎝ RT ⎠
⎛ ΔS*A ·TAo ⎞
point of inflexion if ⎜⎜ − 2 ⎟⎟ = 0
⎝ RT ⎠
ΔSA* ·TAo
i.e. for T =
2R
and this T is ≤ TAo if ( ΔS*A / 2R ) ≤ 1

210:5 solubility of anthracene in benzene

Anthracene (A) + benzene (B)
condition μ Asol = μ Aliq
substitution recipes, assuming ideal liquid mixing:
G*Asol (T ) = GA* liq (T ) + RT ln X A
RT ln X A = −ΔG*A (T ) = ΔS*A (T − TAo )
X = 0.0106; 1 mole per cent.
NB This is equivalent to calculating the anthracene liquidus in the system
anthracene + benzene.
Observe that the same result will be obtained for any B that mixes ideally with A.
370 Solutions

210:6 from TX to PX
A = n-pentane B = n-hexane
normal boiling points TAo = 308.75 K TBo = 341.15 K
heat of vaporization ΔH *A = 2945 R · K ΔHB* = 3343 R · K
equil. vap pressures at 60°C with Clapeyron’s equation:
PAo = 2.01 bar PBo = 0.79 bar

2.0 L

P/bar

1.0

0 X 1

210:7 narrow two-phase regions?

Assuming ideal-mixing behaviour in each of the three forms one can write, e.g.,
* hcp
GEr + RT ln X hcp = GEr
* liq
+ RT ln X liq
* *
X hcp ΔGEr ΔSEr
which gives rise to ln = = (T − TEro ) .
X liq RT RT
At the three-phase equil. temp (1456°C) Xliq is about 0.45, as a result Xhcp is
calculated as 0.476.
This is really a borderline case of drawing a phase diagram with open two-phase
fields.

210:8 heteroazeotrope
Thermodynamically, the case is analogous to the simple eutectic phase diagram,
Figure 3. The answer is found by means of Equations (18) and (19). The
temperature of the heteroazeotrope given by the Handbook is 84.1 oC.

210:9 the ortho and para forms of H2

• Boiling points: para 20.28 K; ortho (by extrapolation) 20.44 K.
Mole fractions at 20.36 K: vapour 0.4947; liquid 0.5053.
• The introduction of the catalyst has no influence: equality of chemical
potentials was already realized by the liquid+vapour equilibrium.
• The set M contains five variables: pressure, temperature, and, for each of
the three phases, the mole fraction of ortho.
The set N shows five signs of equality between the six chemical potentials:
(ortho sol =para sol) = (ortho liq = para liq) = (ortho vap = para vap).
The system is invariant: f = M − N = 5 − 5 = 0.
Solutions 371

211 non-ideal systems - geometrically

211:1 validation of linear contributions

ΔG'
e G β ( X β = X eβ ) + C · X eβ − Gα ( X α = X eα ) − C · X eβ Δ eG
= β α
= +C
Δ X Xe − Xe Δe X
e
α
⎛ ∂G' ⎞ ⎛ ∂Gα ⎞
⎜ α ⎟
=⎜ α ⎟ +C
⎝ ∂X ⎠ X α = Xeα ⎝ ∂X ⎠ X α = X eα

⎛ ∂G' β ⎞ ⎛ ∂G β ⎞
⎜ β ⎟
=⎜ β ⎟
+C
⎝ ∂X ⎠ X β = X eβ ⎝ ∂X ⎠ X β = X eβ

if the original functions Gα and Gβ satisfy the conditions for X eα and X eβ , then the
functions G’α and G’β will also satisfy the conditions for X eα and X eβ

211:2 from G-curves to phase diagram

L V
L

P P T L
V V

X X X

liq a b a
vap c c a

211:3 metastable extensions

For instance for the situation below the three-phase equilibrium temperature

γ γ
α α

β β

the metastable equilibria the stable equilibrium

The points of contact, on the G curves of α and β, of the “metastable common

tangent lines” have inward positions with respect to the points of contact of the
‘stable common tangent line’.
372 Solutions

211:4 isothermal solid+vapour equilibrium

SA + SB

o V + SB
PA
P
V o
PB

0 X 1
NB See also Figure 006:2.

211:5 phase diagram for given ROD and EGC

V + L II

LII
LI LI + LII
T

0 X 1

211:7 phase diagram for EGC and two ROD’s

Solutions 373

211:8 overlapping two-phase regions

β
β
tangent

lines

γ
γ+ α
α
β

γ α

See also Exc.005:6

211:9 the system formulation for a symmetrical binary system

I II
* SOL
GD
L D
f = M [T, P, Xliq I] − N [GD*sol = Gliq ; (∂Gliq/∂X) = 0 ] = 3 − 2 = 1

211:10 azeotropy and Gibbs-Duhem

After subtraction:
(1 − X ) ⎡⎣dμ Avap − dμ Aliq ⎤⎦ + X ⎡⎣ dμBvap − dμBliq ⎤⎦ + (S vap − S liq )dT = 0

Along the liquidus and the vaporus A’s chemical potentials change, but invariably
have the same value: the difference between the changes in vap and liq, as a
result, is zero (same for B’s potentials). For the special case of equality of
composition, therefore, dT = 0.
If the compositions are not equal, one has, after subtraction, for A’s potentials

(1 − X vap )dμ Avap − (1 − X lliq )dμ Aliq , which is not equal to zero.

212 non-ideal systems - analytically

212:1 spinodal and binodal for a trigonometric excess function

RTspin (X) = 4 · C π2 X (1 − X) sin 2 π X
binodal points at zero Kelvin: XI = 0; XII = 0.715
TC = 948.5 K; 0.75 TC = 711 K: XI = 0.132; XII = 0.469; XC = 0.298
374 Solutions

212:2 small solid-state solubility

A B X BI X AII

NaCl + KCl 0.042 % 0.56 %

NaCl + RbCl 16 ppb 6 ppm

212:3 conditions imposed on excess enthalpy and entropy

u c p A > 0 (positive excess enthalpy); A/θ > −2R
lcp A<0 (negative excess enthalpy); A/θ < −2R

212:4 ’re-entrant region of demixing’

T /K ω / 2RT SE HE

R · X (1 − X) RK · X (1 − X)

600 1.300 −7.40 −2880

1.125 −5.55 −1815

500 1.000 −4.00 −1000

0.925 −2.75 −405

400 0.900 −1.80 0

0.925 −1.15 245

300 1.000 −0.80 360

0 X 1 1.125 −0.75 375

200 1.300 −1.00 320

ω = (5 − 0.016 T + 0.00002 T2) RT

The excess heat capacity is given by − X(1−X) .RT . (2b + 6cT)

212:5 indirect evaluation of heat of mixing

ln P vs. X diagram : G E ( X = 0.4; T = 308.35 K ) = −577 J·mol-1
T vs. X diagram : G E ( X = 0.4; T = 337.5 K ) = −463 J·mol-1
HE (X = 0.4; T ≈ 323 K) = −1783 J·mol-1

212:6 isothermal EGC for change from solid to liquid

(1 − X )·PAo ·ΔVA* + X ·PBo ·ΔVB* G E sol ( X )

PEGC ( X ) = +
(1 − X )ΔVA* + X ΔVB* (1 − X )ΔVA* + X Δ VB*
Solutions 375

212:7 types of phase diagram

type of EGC absence of ROD presence of ROD

0 [0] [p]

+ [+] [p +]

− [−] [e] [−p]

−+ [− +] [e +] [− p +] [p − +]

For details, and a further extension, see Oonk and Sprenkels (1969)

212:10 the pressure above which mixed crystals are stable

∆A’s value is −13 kJ.mol-1.
The EGC in the PX plane runs from −1.07 kbar at X = 0, through its maximum at
X = 0.535; P = 3.87 kbar to P = 0.00 kbar at X = 1.
The stable part of the phase diagram is above P = 0; at the NaCl side, the EGC
intersects P = 0 at X = 0.062, the compositions of the coexisting solid and liquid
phases being about 0.03 and 0.11, respectively (see Exc 213:6).

212:11 heat effects derived from phase diagrams

D, and L, heat of melting about 19 kJ.mol-1;
DL (composed of 0.5 D and 0.5 L), heat of melting about 28 kJ.mol-1;
Heat effect of racemization : (−56 +38 = −18) kJ.mol-1.

212:12 a rule of thumb for minimum azeotropes

The absence of a minimum is equivalent to the property that the EGC emanates
from the lower boiling point, which is the boiling point of the first component, with a
positive slope. It implies that Ω may not exceed a certain value. The non-
interference of the region of demixing comes down to a second condition, which is
Ω < 2RTAo .

213 non-ideal systems – numerically

213:1 Chanh’s data set

g1 = (19729 − 9.13853 T /K) J.mol-1; and g2 /g1 = 0.2.
This result is quite close to the real properties.
The last sentence could be rephrased to “Generally, and in general terms, TX
phase diagrams are capable of providing the true Gibbs energy function for their
mean temperature, but not - or only exceptionally, and probably depending on the
structure of the data set and the mathematical model used - the precise change of
the Gibbs energy with temperature”.
376 Solutions

NB. For the data set by Bunk and Tichelaar, Table 2, a physically realistic solution
is obtained in terms of the model with three h and two s parameters (Oonk 1981).

213:2 excess function constants from critical coordinates

a1 = ( −1 + 6 X − 6 X 2 ) / ⎡⎣ 4 X 2 (1 − X )2 ⎤⎦ ; a2 = (1 − 2 X ) / ⎡⎣12 X 2 (1 − X )2 ⎤⎦ , where X is

short for XC.

The uncertainties in g1 and g2 reach values of 1 kJ·mol-1.

213:3 analytical check

RT ln X liq = RT ln X sol − ΔHB* + TΔSB* + (1 − X sol )2 ⎡⎣ 2135 + 429(1 − X sol )⎤⎦ J·mol−1 .

The mean absolute difference between the calculated mole fractions of the liquid
phase and those in the first column of Table 4 is just 0.0012.

213:5 elementary analysis of isothermal liquid+vapour data

In rounded values: g1 /RT = 0.36; g2 /RT = -0.10; ΔP = 1 Pa; ΔX = 0.006

213:6 an application of LOOP

0.0273 (solid) and 0.1128 (liquid).

213:7 an application of ROD

Starting values 0.005 and 0.968; final values 0.00505 and 0.96795.

213:8 unilateral region of demixing

RTspin(X) = BX(1−X)n-1(2n−nX−n2X); the critical mole fraction follows from
dTspin /dX=0, which gives rise to an equation which is quadratic in X.

213:9 unilateral ROD in SiO2 + MgO

n = 3.5; B(2240 K) = 40.2 kJ.mol-1; B(1987 K) = 52.6 kJ.mol-1; points of contact at
double tangent XI = 0.021; XII = 0.402; h = 150 kJ.mol-1; s = 49 J.K-1.mol-1.

213:10 an amusing side-effect

Obviously, in the vicinity of the two maxima there are two regions of demixing,
separated from one another. The inner boundaries of these two ROD’s, the inner
parts of the two binodals, intersect at a temperature above the spinodal’s
intermediate minimum. That temperature is the one at which three phases are in
equilibrium. Below the three-phase temperature the stable equilibrium is between
the two outer phases.
Instructive GX sections, all having four points of inflexion, are for the three-phase
temperature, and for temperatures just above and below it.
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 SUBJECT INDEX

Absent notation 154, 172

Absolute entropy 114, 140ff, 214
Absolute temperature 11
Absolute zero 12
ABΘ model 220, 279ff, 294, 302ff
Activity; - coefficient 216ff, 220ff, 234, 236
Adiabatic 106
Adiabatic change 102
Adiabatic compression 102,105
Altimeter; altitude 40, 196
Amount of phase 18, 24, 26, 57, 73, 74, 84
Amount of substance 13, 18
Annealing 304
Antoine equation 40, 165
A priori equilibrium conditions 7, 20,131
Arc representation 160ff
Avogadro constant 13, 115, 206
Avogadro’s law 76
Auxiliary quantity 121ff, 190
Azeotrope; azeotropy 64, 66, 72, 278, 297

Barometric formula 14, 17, 196

Barothermometry 175
Binary subsystem 52
Binary system 41ff
Binodal 60, 224ff, 227, 268ff, 283, 294, 302ff
Binodal equation 227, 283
Boiling curve 7, 32, 223
Boltzmann relation 115, 207, 228
Bomb calorimeter 112
Bulk modulus 150

Calculation of phase diagrams 299ff

Calorimetry 99, 306
Carnot cycle 103
Celsius temperature scale 11ff, 37
Change in molar entropy 30, 158ff
Change in molar volume 30, 158ff
Characteristic function 121ff, 192
Characteristics of equilibrium 7
Chemical energy 107ff
Chemical equilibrium 76ff, 134ff, 137, 168ff, 193
Chemical formula 13, 28
390 Subject index

Chemical potential 4ff, 82, 131, 151, 190ff, 198, 209

Recipe for - 21, 77, 79, 131, 162, 209, 231ff,
281, 305
Chemical reaction 76ff, 141ff, 168ff
Chiral molecule 35, 47
Cigar-type of phase diagram 41
Clapeyron equation 30ff, 37, 46, 55, 157ff
Classroom experiment 60, 221, 251
Clausius-Clapeyron equation / plot 31, 85, 158ff, 249
Closed region of demixing 277
Closed system 129,192
Common tangent line 299, 203, 215, 264
Compensation temperature 281
Component 19ff
- in the sense of the phase rule 83, 86
Composition variable 15ff
Composition triangle, see Gibbs triangle
Compound 47, 144, 271ff, 290ff, 296
Congruently crystallizing - 74
Congruently melting - 59
Incongruently crystallizing - 74
Incongruently melting - 59, 271ff
Compressibility 104, 145, 149, 150
Compression of ideal gas 103, 104
Computer program 299, 315
Concentration 79
Conservation of energy 107
Conservation of mass 15, 183
Convex curve 201, 206
Cooling curve 57, 68, 71, 307
Criterion for equilibrium
see under Equilibrium
Critical point 31, 223ff, 230, 282
Critical pressure 223
Critical temperature 223ff, 230, 282ff, 311, 314
Cross-differentiation identity 89ff, 94, 96, 113, 121, 191
Crossed isodimorphism 49, 274
Crystal structure 32ff, 43
Crystallization 36, 57, 68ff, 74
Crystallization curve 70
Crystallographic unit cell 149
Cubic expansion coefficient 104, 106, 124, 145
Curie temperature 34
Cylinder-with-piston 24, 76, 96,104, 129
Subject index 391

Data 139ff
Data processing exercise 38, 40, 72, 84, 118, 149, 167, 177,
187, 189, 251, 260, 295, 311,
312, 314
Decoration of symbols 162
Degree Celsius 11
Degree of dissociation 85
Degree of freedom 21,164
Demixing 282
Dependent reactions 172ff
Differential; - coefficient 89ff, 123, 125
Differential expression 90, 94
Differential Scanning Calorimetry 36
Differential Thermal Analysis 69
Dilute solution 64, 231ff, 237ff, 245ff
Dimensionless parameter / quantity 34, 214, 280
Distillation 64ff, 72, 73
Distillation lines 66
Distribution / partition; - coefficient; - law 63, 160, 247
Double tangent line 226, 299
Drop calorimeter 99

Efficiency 103
EGC diagram 261, 275, 277
Electrochemistry 168, 195
Elementary entity 13
Enantiomorphism 33, 156
Energy 93ff, 97, 123
Chemical - 107ff
Conservation of - 107
Enthalpy 97ff, 102, 123, 127
as characteristic function 127
Enthalpy of formation 108, 110, 141
Enthalpy of melting, see Heat of melting
Enthalpy of reaction, see Heat of reaction
Enthalpy-entropy compensation 281
Entropy 12, 30, 114ff, 118
as criterion for equilibrium 128ff
- change in spontaneous event 116, 120
- change with pressure 122
- change with temperature 123
- change with volume 122, 126
microscopic interpretation 115
Entropy change at transition 30, 34ff, 46, 170
Entropy of melting 34, 239, 256
Entropy of vaporization 34, 260
392 Subject index

Equal-G Curve 268ff, 279, 284ff, 296, 302ff

and type of phase diagram 287ff, 296
Equal-G curve equation 284, 286, 296, 308
Equation of state 92, 123, 126, 137, 146
Equilibrium 3ff
Criterion for - 128ff, 138, 192ff, 230
Equilibrium between phases
in non-reacting systems
Liquid + Liquid 18, 52, 60, 63, 72, 290ff, 314
Liquid + Solid 4, 43ff, 53, 54, 57, 68ff, 72, 74, 132,
137, 257, 303ff
Liquid + Vapour 6, 10, 15, 18, 19ff, 25, 26, 27, 31, 40,
42ff, 52, 61, 64ff, 72, 73, 138, 158ff,
165, 234, 254, 265ff, 276, 278, 284ff,
296, 312
Solid + Solid 33, 43ff, 166, 294, 304ff, 311
Solid + Vapour 62, 72, 158ff, 165,167
Liquid + Liquid + Solid 50
Liquid + Liquid + Vapour 66, 277
Liquid + Solid + Solid 38, 39, 49, 50, 53, 68, 74, 277
Liquid + Solid + Vapour 8, 27, 38
Solid + Solid + Solid 38, 50
Solid + Solid + Vapour 62ff, 276
Liquid + Liquid + Solid + Solid 278
Liquid + Solid + Solid + Solid 69
Equilibrium conditions 7, 77ff, 168ff, 193, 203
see also A priori equil. cond.
see also Set N of conditions
Equilibrium constant 78ff, 160, 177
change with pressure 84
change with temperature 79
Equilibrium curve in PT diagram 134, 151ff, 169ff
Equilibrium vapour pressure 15, 38, 158ff
Euler’s criterion 91
Euler’s theorem 186, 191, 204
Eutectic three-phase equilibrium 45, 49, 50, 271ff, 288
Eutectic type of phase diagram 45, 258
Eutectoid 50
Excess chemical potential 213, 216, 235, 281, 305
Excess enthalpy; see also Heat of mixing 209, 212, 220, 221, 280, 295
Excess entropy 212, 280, 295
Excess Gibbs energy 212ff, 220, 279ff, 300ff, 314, 315
Excess heat capacity 293, 295
Excess volume; see also Volume change on 213
Expansion coefficient 104
Expansion of ideal gas 101ff
Extensive quantity 184
Subject index 393

Extra interaction 42ff, 293

Extraction 72

Fahrenheit temperature 18
First Law of Thermodynamics 94ff, 121
First-order transition 34
Fixed point 11
Form 28
Formation property 109, 110, 111, 141ff
Fractionating column 66, 72
Free energy; see Helmholtz energy
Free enthalpy; see Gibbs energy
Freezing point depression 238, 258
Fugacity 137, 250
Function of state 94, 97,113
Fundamental equation 121ff, 198

Gas constant 12, 89, 115, 222

Gibbs-Duhem equation 186, 191, 198, 205, 210, 220, 236
Gibbs energy 121ff, 142ff, 206ff, 211ff
as characteristic function 123, 126
as criterion for equilibrium 130ff, 201ff
- change with pressure 139, 142ff, 152
- change with temperature 139, 142ff, 152
Extrapolation of - 142ff, 148, 149, 150
Molar - 131, 197ff, 281ff, 300
- of ideal gas 131
Gibbs energy of formation 137, 142
- from the oxides 111, 176
Gibbs energy surface 151
Gibbs energy vs. mole fraction diagram 201ff, 207, 212, 215, 218, 226, 263ff
Gibbs’s Phase Rule 22
Gibbs triangle 50, 59
Glass transition 35
Graphical integration 118
Gravitational work 196

Heat 93ff, 97ff

Heat capacity 34, 97ff, 126
- at constant pressure, CP 98, 100, 124, 143
change with pressure 126
- at constant volume, Cv 98, 124
- change 162, 166
Relation between Cv and CP 102, 127
Specific - 98
Heat-capacity plot 35
394 Subject index

Heat effect 31, 78ff, 82, 97

Heat of combustion 112
Heat of melting 34, 115, 165, 215, 239
Heat of mixing 9, 209, 220, 221
Heat of reaction 82, 85, 107ff, 141
Heat of solution 251
Heat of sublimation / vaporization 34, 82, 158ff
Heat of transition 143
Heat pump 104
Heat theorem 115
Helmholtz energy 121, 123, 138, 229, 230
Henry’s Law; - constant 234ff, 246
Henry’s Law region 234
Hess’s Law 108
Heteroazeotrope 262, 297
Heterogeneous chemical equilibrium 80ff, 134
Heterogeneous equilibrium 6
High-pressure form 29
High-temperature form 30
Homogeneous function 186, 188, 192, 204
Homogeneous mixture 190

Ideal dilute solution 231ff, 236, 237ff, 245ff

Ideal equilibria 252ff
Ideal gas 12, 31, 89, 92, 93ff, 101ff, 113, 131,
136, 145, 206, 222
Ideal-gas equation 12, 89ff, 241
Ideal-gas mixture 206ff
Ideal-gas temperature / thermometer 12
Ideal mixture 205, 206ff, 208ff, 219, 222, 252ff
Idealized model / treatment 31, 82, 158, 253
Imperfections in phase diagrams 55
Impurity 65, 68, 72, 74
Inflexion point 258, 260, 281
Integral molar quantity 198, 204
Integral volume 185, 187
Integrating factor 91
Intellectual device 24
Intensive variable / property 10ff, 77
Interaction between molecules 41ff, 222ff
Interaction parameter 223, 259
Intercept of tangent line 199
International System of Units 13
International Temperature Scale 12
Invariant equilibrium 28
Invariant point 172
Invariant triangle 51
Subject index 395

Ionic radius 44ff

Irreversibility 32
Irreversible change 32, 117, 128ff
Isobaric circumstances 23, 41ff
Isochoric change 332
Isodimorphism 48
Isolated system 116, 128
Isopolymorphism 48
Isothermal circumstances 23, 41ff
Isothermal compressibility 104, 124, 145, 150

Joule’s experiment 101

Joule-Thomson coefficient 126

Kinetics 141, 168

Konowalow’s rules 47, 55
Kritchevsky-Kasarnovsky equation 250

Lambda transition 34
Lever rule 24, 25, 69, 202
Linear contribution 214ff, 226, 264, 275, 282, 299ff
Liquidus 42, 211, 252ff
Liquidus equation 253, 255, 259, 260, 290, 292, 296
Liquidus surface 21, 52, 69
Lower critical point 282
Low-pressure form 29
Low-temperature form 30

Magic formula 222ff, 231, 279ff

Magnetic transition 34, 40
Mass fraction 15
Maximum in phase diagram 42, 64
Maximum number of phases 28
Maxwell relations 122, 125
Mechanical equilibrium 3ff
Mechanical potential 3, 30, 113
Melting curve 7, 30
Melting point 115
Mercury thermometer 81
Mesostate 32
Metastability 32, 153
Metastable boiling point 38
Metastable equilibrium 32, 38
Metastable extension 32, 38, 39, 50, 56, 155, 174, 276
Metastable form 32, 141, 153
Metastable melting loop 49
Metastable melting point 32, 49, 153
396 Subject index

Metastable transition point 153

Metastable triple point 38, 154
Metastable two-phase region 49
Metatectic 50
Microscopic configurations 115
Minimum in phase diagram 42, 64
Minus one identity 124, 126
Miscibility gap, see Region of demixing
Mismatch in size 44
Mixed crystals 43, 49, 70, 297
Molality 72, 233, 250
Molar Gibbs energy 82, 192, 197ff, 263, 281ff, 300
Molar mass 13, 15, 183, 244
Molar quantity 197ff
Molar volume 30, 183ff
Molecule 28
Mole fraction 15, 41ff, 185, 192, 197ff
Monatomic ideal gas 99, 118
Monotectic 50
Monotropism 33, 39, 156, 164
Mother liquor 74
Multicomponent mixture 16, 184

NaCl-type of structure 43
Natural variables 122, 130, 192
Natural zero point 11, 115, 139
Nernst’s distribution / partition law 63, 247
Neutral interaction 41ff, 64
Non-ideal dilute solution 233
Non-ideal gas 222
Non-ideal mixing 211ff
Non-ideal mixture 222
Non-ideal systems 263ff, 279ff, 299ff
Non-stoichiometric compound 48
Normal boiling point 11, 38
Normal freezing point 11, 37
Number of components 22ff, 83ff
Number of degrees of freedom 21ff, 83ff, 237ff, 245ff, 252
Number of phases 22ff, 83ff

Open system 190ff

Optical antipodes; Pair of - 35, 47, 64, 278
Optically active substance 35, 47
Orientational freedom 32
Osmotic coefficient 234
Osmotic laws 242
Osmotic pressure 240
Subject index 397

Overall composition 24, 264

Overlapping two-phase regions 44, 49, 58, 278

Partial derivative 89ff

Partial differential 90
Partial molar Gibbs energy 191
Partial molar quantity 183ff, 190ff, 205
Geometric representation of - 199
Partial pressure 78
Partial volume 183ff
Partition / distribution; - coefficient; - law 63, 72, 160, 247
Peritectic type of three-phase equil. 49, 50, 274, 275, 288
Peritectoid 50
Phase 6, 19ff, 28
Phase diagram; see Equilibrium between
Phase diagram analysis 304ff
Phase diagram calculation 299ff
Phase rule 22ff, 83ff
Physical significance 306, 311
Plastic crystals 32
Plate number 66, 72
Point of horizontal inflexion 296
Point of inflexion in G-curve 226, 281
Polymorphism 32, 155ff
Power series 232
Pressure 3ff
Pressure coefficient 124
Pressure units 14
Principal law of hydrostatics 15
Principle of minimal Gibbs energy 130ff, 201ff
Pure substance 28ff, 151ff, 231

Quasiracemate 47

Racemate, Racemic compound 47, 271, 273

Raoult’s Law 46, 234ff, 238
Raoult’s Law region 234
Reaction energy / enthalpy 108
Reciprocal system 58
Redlich-Kister expression 214, 299ff
Re-entrant behaviour 33, 295
Region of demixing 43, 60, 224ff, 268ff, 277, 302ff, 311,
314
Reversibility 32
Reversible change / experiment 93ff, 113, 121, 190
Richard’s rule 34, 256
398 Subject index

Sackur-Tetrode equation 116, 118, 148

Saddle point 52, 66
Saturated solution 61, 246
Saturation 18, 61ff, 72, 75, 251
Schreinemakers’s rule / theorem 56, 66,174
Schreinemakers analysis 175,179
Second Law of Thermodynamics 12, 114, 121
Second-order transition 34, 167
Separation 64
Set M of variables 20ff, 131, 151
Set N of conditions 20ff, 131, 151, 203
Simple eutectic diagram 258, 271
Simple model for unary systems 155ff
- for chemical reactions 172
Single-phase field 30, 51
SI-unit 13ff, 95
Slope of curve in PT phase diagram 30, 157ff, 171
Slope of curve in PX / TX phase diagram 45ff, 240, 244, 260
Solid-state miscibility / solubility 48, 294
Solidus 71, 244, 303, 307ff, 312
Solubility curve 74
Solubility in deep-ocean water 250
Solubility of gas / solid in liquid 72, 246ff, 260
Solute 231ff, 245ff
Solute laws 245ff
Solvent 61, 231ff, 237ff
Solvent laws 237ff
Spinodal 227, 230, 279, 283ff, 294, 302ff,
315
Spinodal equation 227, 284
Spontaneous change 3ff, 29, 32, 116, 128ff, 168, 201
Stable form 33, 141
Stability diagram 174
Stability field 8, 174
Standard Gibbs energy change 78
Standard pressure 143
Standard state 218, 233
Stationary point 47, 55, 266
Steam distillation 68, 73
Stepwise distillation 66
Stirling’s formula 119, 208
Stoichiometric coefficient 194
Storage of thermal energy 251
Substance 13
Subsolidus miscibility 48, 307
Supercooled liquid 32, 35
Subject index 399

Supercooling 70
Supercritical fluid 40, 224, 229

Surface in GPT space 151

in PTX space 41
in TXY space 51
Symmetry 278
System formulation 21, 26, 41, 44, 51, 77, 81, 151,172,
252ff, 262, 269, 290

Tables 139ff, 147, 148

Taylor’s series 145
Temperature 3ff, 11ff
Temperature scale / unit 11ff
Temperature versus volume diagram 57
Ternary from binaries 52ff, 59
Ternary system 50ff, 205
Thermal analysis 36, 80
Thermal equilibrium 3ff
Thermal potential 3ff, 30, 113
Thermobarometry 39
Thermochemical calorie 95
Themodynamic table 139ff, 146
Themodynamic temperature 11ff, 30
Thermogram 36
Third Law of Thermodynamics 115
Three-phase equilibrium 44ff, 50, 268ff, 288ff
Three-phase equilibrium line 44ff, 269
Three-phase triangle 52
Tie line 52, 67
Total differential ` 90, 121, 125, 139
Total Gibbs energy 205
Translational freedom 32
Trigonometric excess function 236, 294
Triple point 7, 12, 29ff
Triple-point coordinates 38
Trouton’s rule 34, 73, 256, 297
Two-phase field / region 51
Type of equal-G curve 289
Type of phase diagram 287ff, 296

Unary system 28ff, 151ff

Unit cell 149, 304
Unit 12ff, 96, 102
Use of superscripts 249
Upper critical point 282
400 Subject index

Vacuum distillation 68, 73

Van der Waals equation of state; - gas 92, 105, 106, 126, 146, 222, 229
Van’t Hoff’s equation; - law 79, 240
Vaporus 42, 236, 252ff, 265ff
Vaporus equation 253, 255
Vaporus surface 21, 52
Vapour pressure 158ff, 165
Vapour pressure lowering 237
Variables; Intensive - 10ff
Variance 21ff
Variance problem 25, 26, 27, 85, 86, 262, 278
Vessel-with-manometer 24, 26
Virtual experiment / change 192ff
Virtual transition point 154
Volume 28
Volume change at transition 30, 46,170
Volume change on mixing 205, 209, 221

Weight percentage 15
Width of two-phase region 64, 253, 256, 261
Work 93ff, 96, 97, 101, 113

X-ray diffraction 304

Zero Celsius 11, 37

Zero line 286, 308
Zero point 11, 37, 115, 139
Zero point for enthalpy 100, 139, 214
Zero point for entropy 115, 139, 214
 SUBSTANCES AND SYSTEMS INDEX

Acetic acid 80, 111

Acetone + chloroform 42, 285ff, 293, 295
Acetone + chloroform + methanol 52
Alcohol, see Ethanol
Aluminium 147
Aluminium oxide 147
Aluminium silicate 39, 179
1-Aminopropane 40, 165
Ammonia 137
Ammonia + hydrogen + nitrogen 76ff, 84, 171, 177,
193, 194
Ammonia + ammonium chloride + hydrogen chloride 80ff, 85, 178
Andalusite + kaolinite + pyrophyllite + quartz + water 179
Aniline + cyclohexane 60
Aniline + water 73
Anthracene + benzene 260
Argon 12, 18, 104

Barium oxide + barium peroxide + oxygen 176

Benzene 243, 244
Benzene + ethanol + water 66
Benzene + n-heptane 312
Benzene + toluene 236
Benzoic acid 112
Benzophenone 154, 164
1,4-Bromochlorobenzene + 1,4-dibromobenzene 48
1,4-Bromochloro- + 1,4-dibromo- + 1,4-dichlorobenzene 54
n-Butane 28

Caesium chloride 166

Calcium carbonate 13, 138
Calcium carbonate + calcium oxide + carbon dioxide 80ff, 134ff, 137, 171
Carbon; see also Diamond, and Graphite 13, 140ff, 166
Carbon + carbon dioxide + carbon monoxide 110
Carbon + carbon dioxide + carbon monoxide +oxygen 171
Carbon + carbon dioxide + oxygen 141ff
Carbon dioxide 38, 111, 147, 229
Carbon dioxide + carbon monoxide + zinc + zinc oxide 86
Carbon dioxide + magnesium carbonate
+ magnesium oxide 176
Carbon disulphide + iodine 63
Carbon monoxide 109, 111, 147
Carbon tetrachloride 32
402 Substances and systems index

Carbon tetrachloride + iodine 63

Carbon tetrachloride + 1,1,1-trichloroethane 49
Carvone 35
Chlorine 110
Chloroform + methanol 47, 52
Chloroform + n-hexane + methylcyclohexane 52
1-Chloro-4-iodobenzene 62
1-Chloro-4-iodobenzene + 1,4-dibromobenzene 62
1-Chloro-4-iodobenzene + naphthalene 62, 72
Copper 12, 99
Copper oxide 147

1-Decanol + 1-dodecanol 42
Diamond 32, 100, 118, 140ff,
166
1,4-Dibromobenzene 62, 165
Dolomite 13
Dysprosium + erbium 261

Ethanol + water 6, 16, 18, 26, 66,

73,187, 221, 240, 293
2-Fluoronaphthalene + naphthalene 48

Gold + palladium 48
Graphite 32, 111, 140ff, 143,
147, 166

Helium 105, 120, 148

Helium + water 250
n-Hexane + methanol + methylcyclohexane 52
n-Hexane + n-pentane 260, 261
Hydrogen 12, 262
Hydrogen + oxygen + water 107ff, 109, 110, 168,
178, 195

Indium 12
Iron 33ff, 40
Isobutylalcohol + toluene 259
(-)- + (+) Isopropylsuccinic acid 45, 47, 297
(-) Isopropylsuccinic acid + (+) methylsuccinic acid 47
(+) Isopropylsuccinic acid + (+) methylsuccinic acid 47
(-)- + (+) Isopropylsuccinic acid + (+) methylsuccinic acid 59

Lithium chloride + potassium chloride 45, 57

Magnesium 147
Magnesium carbonate 13, 111, 176
Substances and systems index 403

Magnesium disilicate 147, 150

Magnesium oxide 147
Magnesium oxide + silica 314
Mercury 12, 14, 114, 118
Methanol 111
Methanol + 1-propanol 259
Methanol + water 205
4-Methylbenzaldehyde + 2-nitro-p-xylene + p-xylene 73

Naphthalene 62, 159, 167

Naphthalene + toluene 27
Nitrogen 105, 137

Oxygen 13, 100, 111, 147

Oxygen + strontium oxide + strontium peroxide 175

Potassium bromide + potassium chloride + sodium

bromide + sodium chloride 58
Potassium chlorate + potassium permanganate + water 74
Potassium chloride + sodium chloride 43, 48, 280, 293, 297,
304ff, 311, 313
Potassium chloride + water 251
Potassium permanganate + water 72

Quartz 13, 111, 147, 149

Rubidium chloride + sodium chloride 44, 294, 312, 314

Rubidium fluoride + sodium fluoride 298

Silica, see Quartz

Silicon 111
Silver bromide 100
Silver oxide 144, 148 109
Sodium 34
Sodium bromide + sodium chloride 244, 307ff
Sodium chloride 118
Sodium chloride + water 18, 189, 220, 242
Sodium sulphate + water 251
Sugar 61
Sulphur 165
Sulphuric acid 96
Sulphuric acid + water 9

Toluene + water 262

404 Substances and systems index

Water 3ff, 11, 30ff, 37, 38,

40, 61, 66, 72, 110,
120, 138, 149, 160,
165, 166, 243
Wustite 48

Zinc 96