Chemistry 163B Winter 2020

Lectures 2-3

Heat and Work

Menu: for TODAY(s)

• Heat (q), Work (w) and the First Law of Thermodynamics

∆U≡q+w

• Example calculations of q, w, U for reversible and

irreversible expansions of ideal gas (comparisons and
‘take home messages’)

• Molecular picture of heat and work energy transfers

2
Chemistry 163B reserve books 2020 (S&E Library) handout #2
a few definitions ,etc. to get us going

• df is ‘differential’ representing an infinitesimal change

final

• to calculate ∆f a finite change ∆f = ∫

initial
df

• if f is a state function, the integral around a closed (cyclic)

path (finish=start) is

∫ df = 0

4
 a few “FACTS OF (thermodynamic) LIFE”

• if the ‘system’ goes from one state to another by differing paths

initial state final state

• the change in some aspect of the system can either be

• independent of the path taken

(depends only on the initial and final values of the state variables)
or
• depend on the path taken

• if change is path independent ⇒ exact differential,

there is underlying STATE FUNCTION

• if change is path dependent ⇒ inexact differential,

no underlying property of the state of system

more in Lecture #5 (math !!) 5

all transfers of energy can be classified as heat (q) or work (w)

We will see (and demonstrate):

• heat (q) and work (w) are NOT PROPERTIES of a system but correspond
to TRANSFERS of energy into (+)sys or out of (−)sys the system
[e.g. there is no underlying property “heat” of a system”]

• when a system goes from an initial to a final state,

e.g. (Pi,Vi,Ti) ⇒ (Pf,Vf,Tf) the values of q and w will DEPEND ON THE
PATH taken between the states

• a small changes in a path-dependent quantities are INEXACT

DIFFERENTIALS indicated by e . g . d− q and d− w

6
the FIRST LAW of thermodynamics E&R4th pp.30, 39-41

• U is symbol for INTERNAL ENERGY of a system

• ∆U=q+w+… ; dU = d− q + d− w + ∑ ... dn i dni=0 closed system,
ignore for now

• ∆Usys=− ∆Usurr (conservation of energy)

• U is state function

• ∆U does not depend on path equivalent

statements
(only on initial and final states)

• dU is an exact differential
7
heat capacity (E&R section 2.11)[4th]

d− q
• C heat capacity [ J K −1 ] extensive
=
dT
the amount (transfer) of heat required to raise substance 1K
d− q
• nC molar heat capacity [ J mol −1 K−1 ] intensive
=
dT
the amount (transfer) of heat requires to raise 1 mol substance 1K

C generally depends on T and conditions

for example ideal monatomic gas

≠
molar heat capacity at constant volume CV = R
2
5
molar heat capacity at constant pressure C P = R
2
3
E= nRT (true !!) but why does it take more heat to raise T at constant P than at constant V ??
2
stay tuned !! 8
transfers of energy: HEAT and work (sec 2.2 )[4th]

change of energy by heat transfer

d− q C=
= dT nC dT (C is extensive,
−q
=q ∫
= d
path
∫
path
nC dT C is intensive)

C will generally depend on T and path

( i .e . conditions )
q > 0 ⇒ energy (heat) gained by system
cools surroundings
(endothermic)
q < 0 ⇒ energy (heat) lost by system
warms surroundings
(exothermic)
9
heat only transfer; thermal equlibrium (also zeroth law; E&R p11) [4th]

initial vacuum
T1, n1,C1 T2, n2,C1

=d-q 1 n=
1C 1dT 1 d-q 2 n 2C 2 dT 2

assume C ' s independent of T

Tf Tf

q 1= ∫ n 1C 1dT =n 1C 1 (T f − T1 ) q 2 = ∫ n 2C 2 dT =n 2C 2 (T f −T2 )
T1 T2

q 1+ q 2 = 0 ⇒ T f = T 1+
n 2C 2 (T 2 − T 1 )
n 1C 1 + n 2C 2

final Tf, n1,C1 Tf, n2,C2 (T1)f=(T2)f=Tf

10
transfers of energy: heat and WORK (sec. 2.3) [4th]

change of energy by work done ON system

energy into system

d− w
= d−- wPV + d− wother e.g. electrical,
gravitational, etc.
derive in a d− wPV = − Pext dV
moment.
wPV
= ∫ d− wPV
= ∫ − Pext dV
path path

w > 0 ⇒ energy gained by system

(work done ON system)
w< 0 ⇒ energy lost by system
(work done ON surroundings)

11
processes: definitions of constraints

• isolated q=0; w=0

• isothermal ∆T=0
• adiabatic q=0
• “against constant
pressure” Pext= const
• reversible process Pint= Pext
a (ideal) process that proceeds so slowly
that an infinitesimal change of conditions
causes the process to proceed in the
opposite (reverse) direction

• irreversible process
all other (real) processes proceeding at finite
rate 12
derivation of w = −P∆V (work of expansion or PV work)

w*surr= work done ON SURROUNDINGS • pressure=force/area

P=F/A ; F= P × A

• ∆V= A × ∆h

• w*surr= Force × Distance

• w*surr= F × ∆h

• w*surr= P × A × ∆h

• w*surr= P × ∆V=P∆V
• want w ≡ work ON SYTEM
• w= − P∆V
to be consistent with
work done ON system
13
ideal gas and energy, heat, work

for IDEAL GAS

• U(≡E) depends ONLY on T (ideal gas, previous class)

• isothermal, ΔT=0,
• ΔU=0=q+w (ideal gas)
• q=-w

• adiabatic: q=0, ΔU=w (in general)

• monatomic ideal gas

• U = (3/2) n RT
• CV= (3/2) n R (∼ prove later)
• CP= (5/2) n R (prove later)
14
work of expansion ideal gas (3 conditions)

P= 10atm P= 1 atm
1 mol 1 mol
T=Tinitial T=Tfinal
Vi = RTi /10atm Vf =RTf /1atm

• isothermal against constant Pext

• adiabatic against constant Pext
• isothermal reversible
• adiabatic reversible (later)

why ??
• understanding of thermodynamic conditions
• how to calculate w=-∫ Pdv
• compare wrev vs wirrev
• AND lots of ‘rewards’ on HW and EXAMS
15
Pressure-Volume work (gene’s lame ‘lifting weights’ analogy to work done against
system is gas inside atmospheric
piston; weights
pressure) are surrounding

P=10 atm isothermal ∆T=0 Pext=1 atm

expansion ΔV

9atm 1atm 9atm 1atm

heat ∆T=0

isothermal expansion against constant pressure (irreversible)

•system is piston and gas inside; weights represent external pressure of surroundings
• Pext=1atm (during volume change) ; ΔVsys > 0; wsys= - P ΔVsys < 0
• work (<0) is done BY SYSTEM ON SURROUNDINGS (1 atm weight lifted)
• E for ideal gas depends only on T
isothermal ideal gas ∆T=0 ⇒ ∆U=0 since w< 0; q= −w > 0 ; heat absorbed by system
16
 Pressure-Volume work (gene’s lame ‘lifting weights’ analogy to work done against
system is gas inside atmospheric
piston; weights
pressure) are surrounding

adiabatic q=0
P=10 atm Pext=1 atm

adiabatic

expansion ΔV

9atm 1atm 9atm 1atm

brr !
adiabatic expansion against constant pressure (irreversible)
• system is piston and gas inside; weights represent external pressure of surroundings
• Pext=1atm (during volume change); ΔVsys > 0; wsys= - Pext ΔVsys < 0
• work (<0) is done BY SYSTEM ON SURROUNDINGS (1 atm weight lifted)
• w< 0; q=0 (adiabatic); Esys(≡Usys)< 0;
energy (potential) of surroundings increases ⇒energy of system decreases⇒gas cools ∆T<0

17
Pressure-Volume work reversible expansion

P=10 atm Pext = 10 atm → 1atm

isothermal ΔT=0
reversible

9atm expansion

1atm 1atm

Vinitial ∆T=0 heat Vinitial

final

• w on surr rev > w on surr irrev (more weights raised in irrev)

• w= − ∫ PextdV

• Pext = Pint = nRT/ V  w= −∫ nRT/ V dV

• isothermal T=const ⇒ w=- nRT ∫ dV/V

w = − nRT ln (Vfinal/Vinitial) 18
wother (E & R p. 32)4th Table 2.1 Types of Work

change of energy by work done ON system

= d− w d− wPV + d− wother
d− w = − Pext dV + d− wother
−
∫
w= − P ∫
ext dV + d wother

Done lifting a h2
weight against Mass (m),
gravity position (h) w = − ∫ m g dh kg m2 s-2 = J

(weight is h1
surroundings)
19
Isothermal expansion: Pext= const ideal gas (irreversible)

Pext=1 atm
P=10 atm isothermal ∆T=0
1atm

expansion ΔV

1atm 9atm 9atm

1mole 1mole
300K 300K
10 atm 1 atm
V1 V2

20
Isothermal expansion: Pext= const; ideal gas; Graphical Interpretation

final

wsystem
= ∫
initial
− Pext dV

=wsystem - Area under Pext − V curve

10 =wsurr Area under Pext − V curve

Pext
(atm) all ΔV against
Pext = 1 atm

V1 V2
V (L)

21
Isothermal expansion: Pext= const ideal gas (irreversible)

Pext=1 atm
P=10 atm isothermal ∆T=0
1atm

expansion ΔV

1atm 9atm 9atm

V final

w= − ∫ Pext dV PV=nRT
1mole Vinitial 1mole
w = -1 atm ( V2 -V1 ) 300K
300K
10 atm
= V2 =
300K R (1mol)
V1
300K R (1mol) 1 atm
V1
1 atm 10 atm V2
 1 1 
w= - ( 300 K-mol )(1 atm ) R − 
 1 atm 10 atm 
w= -2244 J= -2.244 kJ
(- sign implies net work done ON surrounding) 22
Pressure-Volume work reversible isothermal expansion; Pext=Pint

Pext = 10 atm → 1atm

P=10 atm
isothermal 1atm

9atm

9atm expansion

1atm

Vfinal

1mole 1mole
300K 300K
10 atm 1 atm
V1 V2

23
 isothermal irreversible vs isothermal reversible:
which does more work on surroundings ??
Pext=1 atm

1at
m
irrev
ΔV wsys= -2244 kJ
P=10 atm
9 wsurr=+2244 kJ
atm

Pext = 10 atm ∆ 1atm

1at 9at
m m
1at
m
rev irrev
9 atm
wsurr ? w
> surr
> <
Vfinal
24
Isothermal expansion: Pext= Pint ideal gas; Graphical Interpretation

10 nRT
Pext =
V
Pext f i nal

(atm) =
w system ∫
i ni ti al
−Pext dV

=w system -A rea under Pext − V curve

1 =w surr A rea under Pext − V curve

wirrev at const Pext

V1 V2
V (L)

25
Pressure-Volume work reversible isothermal expansion; Pext=Pint

Pext = 10 atm→1atm

P=10 atm
isothermal ΔT=0 1atm

9atm

9atm expansion

1atm
Vfinal
nRT
w=- ∫
Vinitial
Pext dV Pext = Pint =
V Vfinal
Vfinal V
nRT 2
1 V
w=- ∫ dV = - nRT ∫ dV= - nRT ln 2
V V V1
1mole
Vinitial V1
1mole
300K R (1mol) 300K R (1mol)
=
300K V2 = V1 300K
1 atm 10 atm
10 atm 10 atm 1 atm
w= - ( 300 K-mol ) R ln
V1 1 atm V2
w= -5743 J= -5.743 kJ
(more work done ON surroundings
by reversible than irreversible; w = -2.244 kJ)
irrev
26
Pressure-Volume work: irreversible adiabatic expansion Pext = constant

P=10 atm adiabatic q=0 Pext=1 atm

1atm
adiabatic

expansion

9atm 1atm 9atm

adiabatic expansion against constant pressure (irreversible)

1mole ∆U =+
0 w=− Pext (V2 − V1 ) =−1 atm 
 nRT2 nRT1 
−
1mole

300K  P2 P1  T2 ? K
Will soon show
10 atm holds for ideal gas
= ∆UnC
= V ∆T
3
nR ( T2 − T1 ) 1 atm
V NOT const 2
V1

V2
 T 300 K  3
−1atm (1mol ) R  2 − =  (1mol ) R ( T2 − 300 K )
 1atm 10atm  2
no q in, less work done
T2 = 192 K w = -1347 J = -1.347 kJ than isothermal (-2.244 kJ)
27
molecular correlates of heat and work for ideal gas

• total energy:
sum of [number of particles in energy level (ν) × energy of that level (ε)]
E=Σn νn εn

• heat only (no work):

redistributes particles among levels
q>0 ⇒ more particles to higher energy levels
q<0 ⇒ more particles to lower energy levels

• P-V work only (adiabatic)

particle in 3D cube:
CHEM 163A DON’T FRET
3h 2
εn ≈ 2
n 2 where n is an integer (1, 2, . . .)
8mV 3
larger volume (w<0) ⇒ energy levels lower and get more closely spaced
smaller volume (w>0) ⇒ energy levels higher and less closely spaced

28
 molecular picture of heat and work:
constant volume heating (E&R p 44-45)4th
He gas in 10 nm ‘box’; 0.2 K He gas in 10 nm ‘box’; 0.3K

n=8 n=8

n=5 n=5

heating of He, constant V

w = 0; q > 0

1. energy levels same spacing: ∆V=0, w=0 (no change in size of box)
2. greater number of atoms in higher energy levels: q> 0 raises U;
3. ∆U>0 (∆E>0)
29
 molecular picture of heat and work:
reversible adiabatic expansion (E&R p Fig 2-10)4th

He gas in 8 nm ‘box’; 0.31 K He gas in 10 nm ‘box’; 0.2 K

n=8

n=8

• for reversible adiabatic expansion (no heat in) populations in levels do not change
• does total energy E=Σniεi and thus temperature increase or decrease ??
brr ! 30
 Figure 2-10 Energy levels for a He atom confined to a one-dimensional box. Boxes are of
length (a) 10.0 nm and (b) 8.00 nm. Circles indicate the probability that the He atom has an
energy corresponding to each of the energy levels at 0.20 K. Each circle indicates a
probability of 0.010. For example, the probability that the energy of the He atom corresponds
to the lowest energy level in the 10.0 nm box is 0.21

isothermal expansion ∆U=0

n=8

n=8

0.20 K 0.20 K
∆T=0 energy levels and occupancies both change
Copyright © 2019, 2013, 2010 Pearson Education, Inc. All Rights Reserved
Menu: for TODAY(s)

 Heat (q), Work (w) and the First Law of Thermodynamics

∆U≡q+w

 Example calculations of q, w, U for reversible and

irreversible expansions of ideal gas (comparisons and
‘take home messages’)

 Molecular picture of heat and work energy transfers

32
 End of

Lectures 2-3