l2 Thermo 23

Reversible change : can be reversed by an innitesimal modication of a
variable
variable
example : thermal equilibrium of two systems with same temperature
variable
transfer of energy as heat between the two is reversible because
variable
if temperature of either system is lowered innitesimally
variable
then energy ows into the system with the lower temperature
variable
If temperature of either system at thermal equilibrium is raised innitesimally
variable
then energy ows out of the hotter system
variable
There is a very close relationship between reversibility and equilibrium:
variable
There is a very close relationship between reversibility and equilibrium:
systems at equilibrium are poised to undergo reversible change
Suppose a gas is conned by a piston and external pressure, pex is set equal
to the pressure, p , of the conned gas
Such a system is in mechanical equilibrium with its surroundings
because an innitesimal change in the external pressure in either direction
causes changes in volume in opposite directions
If external pressure is reduced innitesimally, the gas expands slightly
If the external pressure is increased innitesimally, the gas contracts slightly
In either case the change is reversible in the thermodynamic sense
If, on the other hand, the external pressure diers measurably from the
internal pressure, then changing pex innitesimally will not decrease it below
the pressure of the gas, so will not change the direction of the process.
If, on the other hand, the external pressure diers measurably from the
internal pressure, then changing pex innitesimally will not decrease it below
the pressure of the gas, so will not change the direction of the process.
Such a system is not in mechanical equilibrium
Calculating work :
For a perfect gas, reversible work

of expansion =
Calculating work :
For a perfect gas, reversible work

of expansion =
VRf VRf
− p dV
ext =− pdV
Vi Vi
= −nRT ln VVfi
for spontaneous expansion :

work= −p (Vf − Vi )
ext
Internal energy (U ) as a function of temperature : U (V , T )
internal energy of a system

increases as temperature is raised
Internal energy (U ) as a function of temperature : U (V , T )
internal energy of a system

increases as temperature is raised
slope of tangent at any
temperature =heat capacity, C
in the Fig.,
C at A < C at B
U (V , T )
U (V , T )
CV dq ∂U

= dT = ∂T V
V
U (V , T )
CV dq U

= dT = ∂∂T V
V
=⇒ dU = CV dT
U (V , T )
CV dq U

= dT = ∂∂T V
V
=⇒ dU = CV dT
If heat capacity is independent of
temperature over range of
temperatures of interest
U (V , T )
CV dq U

= dT = ∂∂T V
V
=⇒ dU = CV dT
If heat capacity is independent of
temperature over range of
temperatures of interest
then ∆U = CV ∆T
∂f ∂f
for f ≡ f (x , y ) df y dx + dy

= ∂x ∂y
x
∂f ∂f

= ∂x ∂y
x
∂f ∂f

= ∂x ∂y
x
▶ large heat capacity =⇒ for given quantity of energy transferred as heat, a
small increase in temperature
▶ phase transition : heat capacity of a sample is innite
mean energy of a molecule due to its translational motion = kB T
3
2
∴ contribution to molar energy = RT

3
2
3
2
∴ contribution to molar energy = RT

3
2
=⇒ considering only translational contribution to internal energy
Um (T ) = Um (0) + RT
3
2
3
2
∴ contribution to molar energy = RT3

2
Um (T ) = Um (0) + RT3
2
For polyatomics, rotational and vibrational contributions must be added :

3
2
∴ contribution to molar energy = RT 3

2
Um (T ) = Um (0) + RT3
2
For polyatomics, rotational and vibrational contributions must be added :

e.g., for CO , Um (T ) = Um (0) + RT + RT + · · ·
2
3
2
Thermodynamic denition of a perfect gas :
no intermolecular interactions in a perfect gas
∴ distance between molecules has no eect on energy
∴ distance between molecules has no eect on energy
=⇒ internal energy of a perfect gas is independent of the volume it occupies
∂U
T =0

∂V
Heat :
dU = dq + dw exp + dwe
Heat :
↑ ↑↗ ↑ ↑
upper lower expansion extra
case case
Heat :
↑ ↑↗ ↑ ↑
case case
generally, we consider only w , dU = dqV

exp
Heat :
↑ ↑↗ ↑ ↑
case case

exp
Heat and work are equivalent ways of changing a system's internal energy
Heat :
↑ ↑↗ ↑ ↑
case case

exp
A system is like a bank: it accepts deposits in either currency, but stores its
reserves as internal energy
Heat :
↑ ↑↗ ↑ ↑
case case

exp
First Law : internal energy of an isolated system is constant
∆U = q + w
Heat :
↑ ↑↗ ↑ ↑
case case

exp
First Law : internal energy of an isolated system is constant
∆U = q + w
dU = dq + dw
Calorimetry
- Constant volume bomb calorimeter : measurement of qV
Calorimetry
`bomb' : central vessel, strong enough to withstand high pressures

Calorimetry
`bomb' : central vessel, strong enough to withstand high pressures

To ensure adiabaticity, calorimeter is immersed in a water bath with temperature
continuously readjusted to that of calorimeter at each stage of combustion
change in calorimeter temperature, ∆T ∝ energy released or absorbed in reaction
measure ∆T =⇒ qV and hence ∆U
measure ∆T =⇒ qV and hence ∆U
Calibration : use a process of known energy output and determine calorimeter

constant
q = C ∆T
Enthalpy
∆energy ̸= energy transferred as heat
when system is free to change its volume
Under these circumstances some of the
energy supplied as heat to system is
returned to surroundings as expansion
work, so dU < dq
Enthalpy
∆energy ̸= energy transferred as heat
when system is free to change its volume
Under these circumstances some of the
energy supplied as heat to system is
returned to surroundings as expansion
work, so dU < dq
def. H = U + pV , a state function
dH = d (U+ pV
) = dU + pdV + Vdp = dq + Vdp =⇒ dqp = dH
dq
def. cp = dT = ∂∂TH p =⇒ dH = Cp dT
p
Hf −Hi qp
Zf Zf
z }| { z }| {
dH = dqp
i i
Hf −Hi qp
Zf Zf
z }| { z }| {
dH = dqp
i i
Part of a constant-pressure
adiabatic ame calorimeter
it is immersed in a stirred
waterbath
Hf −Hi qp
Zf Zf
z }| { z }| {
dH = dqp
i i
Part of a constant-pressure
adiabatic ame calorimeter
it is immersed in a stirred
waterbath
Combustion occurs as a known amount of reactant is passed through to fuel the
ame, and the rise of temperature is monitored.
solved problem :
when 1.0 mol CaCO as calcite converts to aragonite, ∆U = 0.21 kJ
3
Calculate ∆H − ∆U when p = 1 bar given densities of solids : 2.71 g cm− and

3
2.93g cm− respectively

3
solved problem :
3

3

3
▶ ∆[H (aragonite)−H (calcite)] = [U + pV ](a)− [U + pV ](c)

= ∆U + p [V (a) − V (c)] = ∆U + p ∆V
solved problem :
3

3

3

= ∆U + p [V (a) − V (c)] = ∆U + p ∆V
▶ Vm for CaCO (100 g)= 34(a) cm 3
3
37(c)
solved problem :
3

3

3

= ∆U + p [V (a) − V (c)] = ∆U + p ∆V
▶ Vm for CaCO (100 g)= 34(a) cm 3
3
37(c)
▶ ∴ p ∆V = 10 Pa× (34 − 37) × 10− m = −0.3 J
5 6 3
solved problem :
3

3

3

= ∆U + p [V (a) − V (c)] = ∆U + p ∆V
▶ Vm for CaCO (100 g)= 34(a) cm 3
3
37(c)
▶ ∴ p ∆V = 10 Pa× (34 − 37) × 10− m = −0.3 J
5 6 3
▶ ∴ ∆H − ∆U = −0.3J (≈ 0.15% of ∆U )
solved problem :
3

3

3

= ∆U + p [V (a) − V (c)] = ∆U + p ∆V
▶ Vm for CaCO (100 g)= 34(a) cm 3
3
37(c)
▶ ∴ p ∆V = 10 Pa× (34 − 37) × 10− m = −0.3 J
5 6 3
▶ ∴ ∆H − ∆U = −0.3J (≈ 0.15% of ∆U )
▶ usually justiable to ignore ∆H − ∆U for condensed phases, except at
very high pressures, when pV is no longer negligible
Ex. Calculate ∆H − ∆U when 1.0 mol Sn(s, grey) of density 5.75 g cm− changes
3
to Sn(s, white) of density 7.31 g cm− at 10.0 bar. At 298 K, ∆H = 2.1 kJ

3
3

3
▶ ∆[H (w)−H (g)] = [U + pV ](w)− [U + pV ](g)

= ∆U + p [V (w) − V (g)] = ∆U + p ∆V
3

3
▶ ∆[H (w)−H (g)] = [U + pV ](w)− [U + pV ](g)

= ∆U + p [V (w) − V (g)] = ∆U + p ∆V
▶ Vm for Sn (118.71 g)= 20.65(g) cm 3
16.24(w)
3

3
▶ ∆[H (w)−H (g)] = [U + pV ](w)− [U + pV ](g)

= ∆U + p [V (w) − V (g)] = ∆U + p ∆V
▶ Vm for Sn (118.71 g)= 20.65(g) cm 3
16.24(w)
▶ ∴ p ∆V = 10 × 10 Pa× (16.24 − 20.65) × 10− m = −4.4 J
5 6 3
3

3
▶ ∆[H (w)−H (g)] = [U + pV ](w)− [U + pV ](g)

= ∆U + p [V (w) − V (g)] = ∆U + p ∆V
▶ Vm for Sn (118.71 g)= 20.65(g) cm 3
16.24(w)
▶ ∴ p ∆V = 10 × 10 Pa× (16.24 − 20.65) × 10− m = −4.4 J
5 6 3
▶ ∴ ∆H − ∆U = −0.44J (≈ 0.2% of ∆U )
enthalpy of a perfect gas:
H = U + pV = U + nRT =⇒ ∆H = ∆U + ∆nRT
solved problem :
Water is heated to boiling under p = 1.0 atm. When an electric current of 0.50 A
from a 12 V supply is passed for 300 s through a resistance in thermal contact
with it,
0.798 g of water is vaporized. Calculate ∆Um and ∆Hm at the boiling point
(373.15 K)
solved problem :
with it,
(373.15 K)
∆H = qp = 0.50 A ×12 V× 300s
∆Hm = qp = .
0 50 ×12×300
0.798 = 41 kJ mol−1
18
solved problem :
with it,
(373.15 K)
∆H = qp = 0.50 A ×12 V× 300s
∆Hm = qp = .
0 50 ×12×300
0.798 = 41 kJ mol−1
18
∆Um = ∆Hm − RT = 38 kJ mol−1 [∵ p (Vg − Vl ) ≈ pVg = RT ]

solved problem :
with it,
(373.15 K)
∆H = qp = 0.50 A ×12 V× 300s
∆Hm = qp = .
0 50 ×12×300
0.798 = 41 kJ mol−1
18
∆Um = ∆Hm − RT = 38 kJ mol−1 [∵ p (Vg − Vl ) ≈ pVg = RT ]

Notice ∆Um < ∆Hm because energy has been used to drive back surrounding
atmosphere to make room for vapour
Enthalpy (H ) as a function of temperature :
internal energy and enthalpy of

system increase as temperature is
raised
Enthalpy (H ) as a function of temperature :
internal energy and enthalpy of

system increase as temperature is
raised
at constant pressure, slope of
tangent at any temperature
=heat capacity, Cp
For gases, at a given temperature
the slope is steeper than that of
internal energy versus
temperature
Cp, m > CV , m
Dierential scanning calorimeter (DSC) measures energy transferred as heat
to or from a sample at constant pressure during a physical or chemical change
'dierential' refers to the fact that the behaviour of the sample is compared to that
of a reference material which does not undergo a physical or chemical change
during the analysis
during the analysis
'scanning' : temperatures are increased, or scanned, during the analysis
during the analysis
DSC consists of two small, separate but identical compartments heated electrically
at constant rate
during the analysis
at constant rate
output : dierence in power needed to

maintain heat sinks at equal temperatures
as temperature rises.
during the analysis
at constant rate
output : dierence in power needed to

maintain heat sinks at equal temperatures
as temperature rises. T (t ) = T + αt ,
0
where T = initial temperature

0
α = temperature scan rate (in Ks − )1
A computer controls electrical power to

maintain same temperature in sample and
reference compartments
sample temperature changes signicantly relative to that of reference material
if transfer of energy as heat occurs in the sample during the scan
sample temperature changes signicantly relative to that of reference material
To maintain same temperature in both compartments, excess energy is transferred
as heat to or from sample during the process
an endothermic process lowers sample temperature relative to that of reference
and, as a result, the sample must be heated more strongly than reference in order
to maintain equal temperatures
If no physical or chemical change occurs in sample at temperature T
heat transferred to sample, qp = Cp ∆T
The chemical or physical process requires the transfer of qp + qp, ex
where qp, ex = excess energy transferred as heat, to attain same change in
temperature of the sample
qp, ex = apparent change in heat capacity at constant pressure, Cp during
temperature scan
temperature scan
heat capacity = Cp + Cp, ex and qp + qp, ex = (Cp + Cp, ex ) ∆T
temperature scan
heat capacity = Cp + Cp, ex and qp + qp, ex = (Cp + Cp, ex ) ∆T
∴ Cp, ex = q∆p Tex
, q
= pα,tex = Pαex ;
Pex = excess electrical power necessary to
equalize the temperature of sample and reference compartments
DSC trace - a thermogram : plot
of Pex or C against T
Broad peaks in thermogram
indicate processes requiring
transfer of energy as heat
TR 2
∆H = Cp, ex dT
T1
.
thermogram for protein ubiquitin
at pH = 2.45
native structure up to ≈ 45◦ C
and then endothermic
conformational change

TR 2
∆H = Cp, ex dT
T1
.
Adiabatic expansion : Ti , Vi −→ Tf , Vf
when a perfect gas expands adiabatically
work is done but no heat enters the system
internal energy falls - kinetic energy of
molecules falls, average speed decreases
∴ temperature falls
∆U for temperature change from Ti to Tf and
the volume change from Vi to Vf can be seen
as the sum of two steps
1st step : only volume changes and
temperature is constant
1st step : only volume changes and
temperature is constant
U for perfect gas is independent of volume of
molecules, the overall ∆U arises solely from
second step, the change in temperature at
constant volume
∆U = Cv (Tf − Ti ) = wad
Adiabatic processes
wad = Cv ∆T
Adiabatic processes
wad = Cv ∆T
reversible adiabatic expansion :
Cv dT = −pdV
Adiabatic processes
wad = Cv ∆T
Cv dT = −pdV
For perfect gas, Cv dT nRdV
T =− V
Adiabatic processes
wad = Cv ∆T
Cv dT = −pdV
T =− V
TR 2 V2
Cv dT = − R nRdV
T V
T1 V1
Adiabatic processes
wad = Cv ∆T
Cv dT = −pdV
T =− V
TR 2 V2
Cv dT = − R nRdV
T V
T1 V1
Cv ln TT21 = −nR ln VV21
Adiabatic processes
wad = Cv ∆T
Cv dT = −pdV
T =− V
TR 2 V2
Cv dT = − R nRdV
T V
T1 V1
CnRv CnRv
or, ln TT21 = ln V T2 =V

1
V2 or, T1 V2
1
Adiabatic processes
wad = Cv ∆T
Cv dT = −pdV
T =− V
TR 2 V2
Cv dT = − R nRdV
T V
T1 V1
CnRv CnRv
or, ln TT21 = ln V T2 =V

V2
1 or, T1 V2
1
nR
T2 = V1 CV = V1 γ−1 or, TV γ−1 = const. label : CRV

T1 V2 V2
show: pV γ = const
p-V-T plots : isotherms and adiabats
pressure declines more steeply for an adiabat than for an isotherm
p-V-T plots : isotherms and adiabats
pressure declines more steeply for an adiabat than for an isotherm
in isothermal expansion, energy ows into the system as heat and maintains the
temperature; as a result, pressure does not fall as much as in adiabatic expansion
ex. :
adiabatic, reversible expansion of 0.020 mol Ar
initially at 25 C, from 0.50 dm to 1.00 dm
o 3 3
ex. :
o 3 3
CV of argon = 12.48 JK− mol− , γ =

1 1 .
12 48 +8.314
.
12 48
= .
20 794
.
12 48
= 1.666
ex. :
o 3 3

1 1 .
12 48 +8.314
.
12 48
= .
20 794
.
12 48
= 1.666
Using Tf Vfγ− = Ti Viγ−
1 1
ex. :
o 3 3

1 1 .
12 48 +8.314
.
12 48
= .
20 794
.
12 48
= 1.666
1 1
we have Tf = 298 × = 188 K

.
0 50
0.666
1
ex. :
o 3 3

1 1 .
12 48 +8.314
.
12 48
= .
20 794
.
12 48
= 1.666
1 1
we have Tf = 298 × = 188 K

.
0 50
0.666
1
∆T = 188 − 298 = −110K and wad = nCv ∆T = −0.020 × 12.48 × 110 = −27 J
ex. :
o 3 3

1 1 .
12 48 +8.314
.
12 48
= .
20 794
.
12 48
= 1.666
1 1
we have Tf = 298 × = 188 K

.
0 50
0.666
1
∆T = 188 − 298 = −110K and wad = nCv ∆T = −0.020 × 12.48 × 110 = −27 J
Note : ∆T is independent of the amount of gas but the work is not
Thermochemistry
Thermochemistry
a reaction vessel and its contents form a system, and chemical reactions result in
exchange of energy between system and surroundings
Thermochemistry
use calorimetry to measure energy supplied or discarded as heat by a reaction
Thermochemistry
identify qV = ∆U or qp = ∆H
Thermochemistry
Conversely, if we know ∆U or ∆H for a reaction, predict the energy (transferred as
heat) the reaction produces
Thermochemistry
exothermic process at constant pressure : ∆H < 0
Thermochemistry
exothermic process at constant pressure : ∆H < 0
endothermic process at constant pressure : ∆H > 0
Standard state :
Standard state :
standard state of a substance at a specied temperature is its pure form at 1 bar
Standard state :
ex. liquid ethanol at 298 K : pure liquid ethanol at 298 K and 1 bar
Standard state :
solid iron at 500 K is pure iron at 500 K and 1 bar
Standard state :
Standard enthalpy change, ∆H ⊖ =
Standard state :
enthalpy of products − enthalpy of reactants
standard states standard states
Standard state :
standard enthalpy of vaporization :

∆ H ⊖ = enthalpy change per mole when a pure liquid at 1 bar vaporizes to a
vap
gas at 1 bar
H O(l)−→ H O(g) ∆ H ⊖ (373K) = 40.66 kJmol−
2 2 vap
1
Standard state :

vap
gas at 1 bar
H O(l)−→ H O(g) ∆ H ⊖ (373K) = 40.66 kJmol−
2 2 vap
1
standard enthalpy of fusion :

∆ H ⊖ = enthalpy change per mole when a pure liquid at 1 bar condenses to
fus
solid at 1 bar
H O(s)−→ H O(l) ∆ H ⊖ (273K) = 6.01 kJmol−
2 2 fus
1
Standard state :

vap
gas at 1 bar
H O(l)−→ H O(g) ∆ H ⊖ (373K) = 40.66 kJmol−
2 2 vap
1
standard enthalpy of fusion :

∆ H ⊖ = enthalpy change per mole when a pure liquid at 1 bar condenses to
fus
solid at 1 bar
H O(s)−→ H O(l) ∆ H ⊖ (273K) = 6.01 kJmol−
2 2 fus
1
standard enthalpies may be reported for any temperature

enthalpy is a state function
∆H is independent of path between the two
states
∆H is independent of path between the two
states
same ∆H ⊖ for change brought about between
same initial and nal states
e.g., conversion of a solid to a vapour either as
occurring by sublimation
H O(s)−→ H O(l) ∆ H ⊖
2 2 fus
H O(l)−→ H O(g) ∆ H ⊖
2 2 vap
H O(s)−→ H O(g) ∆ H ⊖ = (∆ H ⊖ + ∆ H ⊖ ) > ∆

2 2 sub fus vap vap H⊖
∆H ⊖ for a forward process and its reverse
dier in sign
∆H ⊖ for a forward process and its reverse
dier in sign
e.g., conversion of a solid to a vapour either as
occurring by sublimation
∆H ⊖ (A → B) = −∆H ⊖ (B → A)
Standard reaction enthalpy :
change in enthalpy for
Pure, separate reactants in standard states −→
pure, separate products in standard states
Ex. CH (g)+2O (g)−→ CO (g)+2H O(l) ∆r H ⊖ = −890 kJ
4 2 2 2
4 2 2 2
For the reaction 2A+B−→3C+D

4 2 2 2

∆r H ⊖ = {3Hm ⊖
(C) + Hm
⊖
(D)} − {2Hm
⊖
(A) + Hm
⊖
(B )}
4 2 2 2

∆r H ⊖ = {3Hm ⊖
(C) + Hm
⊖
(D)} − {2Hm
⊖
(A) + Hm
⊖
(B )}
generally, ∆r H ⊖ = ν Hm
⊖
ν Hm
⊖
P P
−
products reactants
4 2 2 2

∆r H ⊖ = {3Hm ⊖
(C) + Hm
⊖
(D)} − {2Hm
⊖
(A) + Hm
⊖
(B )}
generally, ∆r H ⊖ = ν Hm
⊖
ν Hm
⊖
P P
−
products reactants
standard enthalpy of combustion, ∆C H ⊖ = standard reaction enthalpy for the

complete oxidation of an organic compound to CO gas and liquid water if the
2
compound contains C, H, and O, and to N gas if N is also present

2
reaction enthalpy in terms of enthalpies of formation
reaction enthalpy in terms of enthalpies of formation
∆r H ⊖ = ν∆f H ⊖ − ν∆f H ⊖
P P
products reactants
Can we construct ∆f H ⊖ from a knowledge of chemical constitution of the species?
Can we construct ∆f H ⊖ from a knowledge of chemical constitution of the species?
no thermodynamically exact way of expressing enthalpies of formation in terms of
contributions from individual atoms and bonds
TR 2
dH = Cp dT =⇒ H (T 2 ) = H (T1 ) + Cp dT assuming no phase transition in
T1
temperature range of interest
TR 2
dH = Cp dT =⇒ H (T 2 ) = H (T1 ) + Cp dT assuming no phase transition in
T1
temperature range of interest
Kirchho's law :
TR 2
∆r H ⊖ (T2 ) = ∆r H ⊖ (T1 ) + ∆r Cp⊖ dT
T1
where ∆r Cp⊖ = ν Cp,⊖m − ν Cp,⊖m
P P
products reactants
solved prob.: ∆f H ⊖ (H O(g);298 K)= −241.82 kJ mol−
2
1
Estimate ∆f H ⊖ at 100 C
o
given C (H O,g)= 33.58 J K− mol− ; C (H ,g)= 28.84 JK− mol− ;

p, m 2
1 1
p, m 2
1 1
C (O ,g)= 29.37JK− mol−

p, m 2
1 1
2
1
Estimate ∆f H ⊖ at 100 C o

p, m 2
1 1
p, m 2
1 1
C (O ,g)= 29.37JK− mol−

p, m 2
1 1
∆r Cp⊖ = C (H O,g)−{C (H ,g)+ C (O ,g)= −9.94JK− mol−

p, m 2 p, m 2
1
2 p, m 2
1 1
2
1
Estimate ∆f H ⊖ at 100 C o

p, m 2
1 1
p, m 2
1 1
C (O ,g)= 29.37JK− mol−

p, m 2
1 1
∆r Cp⊖ = C (H O,g)−{C (H ,g)+ C (O ,g)= −9.94JK− mol−

p, m 2 p, m 2
1
p, m 2
1 1
∴ ∆r H ⊖ (T2 ) = ∆r H ⊖ (T1 ) + (T2 − T1 ) ∆r Cp⊖

2
= −241.82 − 75 × 9.94 × 10−3 = −242.6kJ mol−1

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Reversible change : can be reversed by an innitesimal modication of a

For a perfect gas, reversible work

For a perfect gas, reversible work

for spontaneous expansion :

internal energy of a system

internal energy of a system

∴ contribution to molar energy = RT

∴ contribution to molar energy = RT

∴ contribution to molar energy = RT3

For polyatomics, rotational and vibrational contributions must be added :

∴ contribution to molar energy = RT 3

For polyatomics, rotational and vibrational contributions must be added :

generally, we consider only w , dU = dqV

generally, we consider only w , dU = dqV

generally, we consider only w , dU = dqV

generally, we consider only w , dU = dqV

generally, we consider only w , dU = dqV

`bomb' : central vessel, strong enough to withstand high pressures

`bomb' : central vessel, strong enough to withstand high pressures

Calibration : use a process of known energy output and determine calorimeter

Calculate ∆H − ∆U when p = 1 bar given densities of solids : 2.71 g cm− and

2.93g cm− respectively

Calculate ∆H − ∆U when p = 1 bar given densities of solids : 2.71 g cm− and

2.93g cm− respectively

▶ ∆[H (aragonite)−H (calcite)] = [U + pV ](a)− [U + pV ](c)

Calculate ∆H − ∆U when p = 1 bar given densities of solids : 2.71 g cm− and

2.93g cm− respectively

▶ ∆[H (aragonite)−H (calcite)] = [U + pV ](a)− [U + pV ](c)

Calculate ∆H − ∆U when p = 1 bar given densities of solids : 2.71 g cm− and

2.93g cm− respectively

▶ ∆[H (aragonite)−H (calcite)] = [U + pV ](a)− [U + pV ](c)

Calculate ∆H − ∆U when p = 1 bar given densities of solids : 2.71 g cm− and

2.93g cm− respectively

▶ ∆[H (aragonite)−H (calcite)] = [U + pV ](a)− [U + pV ](c)

Calculate ∆H − ∆U when p = 1 bar given densities of solids : 2.71 g cm− and

2.93g cm− respectively

▶ ∆[H (aragonite)−H (calcite)] = [U + pV ](a)− [U + pV ](c)

to Sn(s, white) of density 7.31 g cm− at 10.0 bar. At 298 K, ∆H = 2.1 kJ

to Sn(s, white) of density 7.31 g cm− at 10.0 bar. At 298 K, ∆H = 2.1 kJ

▶ ∆[H (w)−H (g)] = [U + pV ](w)− [U + pV ](g)

to Sn(s, white) of density 7.31 g cm− at 10.0 bar. At 298 K, ∆H = 2.1 kJ

▶ ∆[H (w)−H (g)] = [U + pV ](w)− [U + pV ](g)

to Sn(s, white) of density 7.31 g cm− at 10.0 bar. At 298 K, ∆H = 2.1 kJ

▶ ∆[H (w)−H (g)] = [U + pV ](w)− [U + pV ](g)

to Sn(s, white) of density 7.31 g cm− at 10.0 bar. At 298 K, ∆H = 2.1 kJ

▶ ∆[H (w)−H (g)] = [U + pV ](w)− [U + pV ](g)

∆Um = ∆Hm − RT = 38 kJ mol−1 [∵ p (Vg − Vl ) ≈ pVg = RT ]

∆Um = ∆Hm − RT = 38 kJ mol−1 [∵ p (Vg − Vl ) ≈ pVg = RT ]

internal energy and enthalpy of

internal energy and enthalpy of

output : dierence in power needed to

output : dierence in power needed to

where T = initial temperature

α = temperature scan rate (in Ks − )1

A computer controls electrical power to

DSC trace - a thermogram : plot

CV of argon = 12.48 JK− mol− , γ =

CV of argon = 12.48 JK− mol− , γ =

CV of argon = 12.48 JK− mol− , γ =

we have Tf = 298 × = 188 K

Reversible change : can be reversed by an innitesimal modication of a

output : dierence in power needed to

output : dierence in power needed to