Fall 2024 CHM 585 (Phys. Chem.

1):
Ch. 2

Chapter 2:
Heat, Work, Internal Energy,
Enthalpy, and the First Law of
Thermodynamics
(Covered: All sections
of this chapter, but
only PV work)
Dr. Elizabeth A. Ploetz
Dr. Paul E. Smith
Department of Chemistry
Kansas State University 1
Copyright © 2019, 2013, 2010 Pearson Education, Inc. All Rights Reserved

Topics Introduced in this Chapter

 Internal energy
 The First Law of Thermodynamics
 Heat
 Work
 Reversible vs. Irreversible Processes
 State Functions vs. Path Functions
 Heat Capacity
 Enthalpy
 Calculations of the above for processes involving ideal
gases.

2
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Copyright 2023, Elizabeth A. Ploetz and

Paul E. Smith 1
Fall 2024 CHM 585 (Phys. Chem. 1):
Ch. 2

Chapter 2:
Heat, Work, Internal Energy,
Enthalpy, and the First Law of
Thermodynamics
(Covered: All sections
of this chapter, but
only PV work)
Dr. Elizabeth A. Ploetz
Dr. Paul E. Smith
Department of Chemistry
Kansas State University 1
Copyright © 2019, 2013, 2010 Pearson Education, Inc. All Rights Reserved

Topics Introduced in this Chapter

 Internal energy
 The First Law of Thermodynamics
 Heat
 Work
 Reversible vs. Irreversible Processes
 State Functions vs. Path Functions
 Heat Capacity
 Enthalpy
 Calculations of the above for processes involving ideal
gases.

2
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Copyright 2023, Elizabeth A. Ploetz and

Paul E. Smith 1
Fall 2024 CHM 585 (Phys. Chem. 1):
Ch. 2

2.1 The Internal Energy and the First Law of

Thermodynamics
Cannot know als energy
• For a thermodynamic process such as the expansion or crl SE a

compression of a substance, what matters is the change

in the energy of the system and surroundings, not the
absolute value of the energy. Ex'
• We only care about the “internal” properties of the HE doesn't change
system, not those due to a particular frame of reference. & if the container
• Ex: KE of water in water bottle on the ground vs. on an moves Only
if mokeles .

airplane relative to an observer on the ground. do

• For thermo calcs, the coordinate system is fixed on the

container.

3
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2.1 The Internal Energy and the First Law of i

S
H

Thermodynamics S
↑
• Internal Energy (U) is the result of various contributions 0
&, -
at the molecular level:
.

H
• Includes:
H

in any directions
• Molecular translational, rotational, vibrational, and more 3

look & KE then T

electronic energy of molecules Z

• Energy related to chemical bonds

• PE of interaction between molecules (intermolecular
energy) HH -
0
-
-
0
-
H
&
encrest
...
H

• Etc. & energy interactions stored in

involved in spinning
• Excludes: KE or PE the system as a whole may have b/c
of its motion or location in an external field (e.g. gravity, O

EM). But it would include contributions of that field to -2

H
Qu

the energy due to the coupling of the internal degrees of Bonds expand /contract
freedom of the system with the field (e.g., crystal which changes Energy
0

deforming if E-field applied). 4 can also change

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-

e to
promote
4 -
another every
level and now

= was more
cneg
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Fall 2024 CHM 585 (Phys. Chem. 1):
Ch. 2

2.1 The Internal Energy and the First Law of

Thermodynamics LIE extensive -
so

Total Energy of = KEmacro + PEmacro + U double sys 2u

•
=

can't calculate watch but

microscopic
,

ignore
changes

• U has both kinetic and potential contributions

• Wait, I thought thermo was a macroscopic science??
• Development of thermo requires no knowledge of the nature
of U, only ways to measure changes in U for a process. We
cannot measure the absolute U.
• Most applications of thermo that we will consider:
• System will be at rest.
• External fields will not be present. (Gravity effects are
usually negligible and are typically ignored – depends on
what you are doing.)
• Changes in KEmacro and PEmacro will be zero.

5
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2.1 The Internal Energy and the First Law of

Thermodynamics

Various types of processes:

• Isothermal: constant
T
T; ∆T=0
0 ; constant temp
=

• Isobaric: constant
P P;; ∆P=0 pressure
= 0 1

• Isochoric: V 0 ; = 11
volume ; constant density

• Adiabatic: constant
NO HEATV; ∆V=0 ; heat (g)
GAINED/LOST

NOTE : Isothermal # a diabatic .

Heat can be absorbed even if temp doesn't change
.

the , but
Bok water : Once you reach
100 you keep the temp same

AT .
0
heat is constantly absorbed from burer to maintain
=

6
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Copyright 2023, Elizabeth A. Ploetz and

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Fall 2024 CHM 585 (Phys. Chem. 1):
Ch. 2

2.1 The Internal Energy and the First Law of

Thermodynamics
• First Law of Thermodynamics is based on our experiences
that energy can be neither created nor destroyed, if the
energy of the Sys and Surr are taken into account.
The internal energy, U, of an
[1st Law of Thermo]
isolated system is constant
• Break isolated Sys into two subsystems:
Utot  USys  USurr  0
[1st Law of Thermo]
USys  USurr
ISOLATED

sorr
DV = 0 >
-
Sys
7
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7
NOTE : DV w/ no subscript refas to the AUsys -

2.1 The Internal Energy and the First Law of

Thermodynamics
• In a closed Sys in which NO chem rxns or phase changes
occur, ∆U can only be due to the flow of heat -energy (q) across
to expansion/contraction
the boundary and/or work (w) done across the boundary.
↓ de

U  q  w [1st Law of Thermo]

Sys if no
subscript. [Closed; No rxn; No phase ∆] Sys
S

Du =

g
+ w Surr

ADIABATIC ISO CHORIC

q = 0 >
- DV = w =0
w - Du =
9

8
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Fall 2024 CHM 585 (Phys. Chem. 1):
Ch. 2

2.2 Heat

• Heat: Quantity of energy that flows across the boundary

between the Sys and Surr because of a T difference
between the Sys and Surr. (no work)
• Characteristics:
• Heat always flows spontaneously from regions of high T
to regions of low T.
• Transitory. Only appears during a change in state of the
Sys/Surr. The heat is changing the state
• Not associated with the initial and final states. (only during 1)
• Heat is a type of energy transfer mechanism.
• q changes in accordance with the First Law.

9
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2.2 Heat

• Signs:
• If no work done and… TfTi
• ∆TSys > 0, then q > 0. Heat withdrawn from Surr.
Tincreased

• ∆TSys < 0, then q < 0. Heat withdrawn from Sys. TfTi

↑ decreased
• U is a monotonically increasing function of T for a uniform,
single-phase system of constant composition. U  T.

DV =
a + =
9 T4 u4

TNUL

10
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Fall 2024 CHM 585 (Phys. Chem. 1):
Ch. 2

2.3 Work : form of energy

• Work (w): any quantity of energy that “flows” across the
boundary between Sys and Surr as a result of a force acting
through a distance.
w =
-

[Pexternal du

NOT
X
ne)
• Characteristics of w:
• Transitory. Only appears during a change in state of the
Sys/Surr. Once you reach final state no work is associated w/sys mlike U
a , :

• Not associated with the initial and final states.

• Work is a type of energy transfer mechanism.
11
• w changes in accordance with the First Law.
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11

*
Za
2.3 Work
↓F

• Quantifying w: Area
aforce If displacement
(A)
Wsys
=
-SFzdz =
) Pext F
=
Pressure

-Sv
-SpextdV
=

Nsys30 when SVC0 (VA) + W when-v

compress

Wsys 10 when Svc0 (14) -

W When V
expand

Vf

w    P ext dV [PV work] => ALWAYS TRUE

Vi -Pinside
• Note: Pext is not necessarily equal to P of system
• Non-PV types of work (stretching, surface
expansion, electrical work) not our focus here. 12
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 Fall 2024 CHM 585 (Phys. Chem. 1):
Ch. 2

2.3 Work

• Signs: in DU Area
NOTE : If you • w>0: wr => Vd(t (A)
compress
• Work done on Sys by Surr
a

gas you introduce

evert
• Force and displacement same direction 7z direction)
,

and o &
• Compression of Sys (v)
• ∆U>0 if adiabatic q = Sw W =0
=

• w<0: w(t) vy >

-

• Work done on Surr by Sys

• Force and displacement opp. directions
• Expansion
• ∆U<0 if adiabatic AN w =

energy disappears from sys to do work

13
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13

Joules
↓
Calculate the work involved in expanding 20.0 L of an
ideal gas to a final volume of 85.0 L against a constant
external pressure of 2.50 bar.
wa >
- Ard

W = -

Sextdv wo - SuL6

2
=
-

[2 .
50dV =
-

2 .

59 20
d

= - 2 .

5[v]
Gas constant
=
= 2 .
5[85 -

20]
R 8 314)/ma/k 65
.

w =
-

2 5 . x
--

R 8 314x10-2Lbar molK"w
. .
= -
162 5 . bar
.

162 5 bar L
(ii)
s
-
.
.

100Sur
-
14
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Fall 2024 CHM 585 (Phys. Chem. 1):
Ch. 2

WATER (00 - ICE (0 %

2.4 Equilibrium, Change, and Reversibility T ↓ lan infinitesimal small

• Two classes of processes: Changes

• Reversible:
WATER (O%) ICELO)
• Sys is in equilib. with Surr throughout the process.
Non-spontaneous (Ch. 5). ↓P Tw * Small Changes to P V T can

• An infinitesimal opposing change in the variable that

, , , ,

change direction of EQ

drives the process would &

cause a reversal in the
direction of the process.
COULD
WATER (100)& ICE(10 )
%

• A process that can be reversed without leaving any

IRRIVERSIBLE
-
can't change by small amount
trace on the Sys or Surr. (Both Sys & Surr can be 19 99 C) has to
°
.
be large (0 )
%

returned to their initial states.)

• Ideal/theoretical limit/”unreachable goal”. Useful for
optimizing/comparing to real processes.
• Deliver the most work (to Surr) possible (car engine;
turbine). Consume the least work (from Surr) possible
(compressor).
• Real processes can approach reversibility. 15
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15

2.4 Equilibrium, Change, and Reversibility

• Two classes of processes:
• Irreversible:
• All other processes. a.k.a. “Real” or “Natural
processes.”
• System is not in equilibrium with Surr throughout the
process. Spontaneous process (Ch. 5).
• Processes are irreversible due to:
• Friction
• Fast/unrestrained compression/expansion
• Finite T differences, leading to heat transfer
• Mixing of fluids
• Electrical resistance
• Chemical reactions
• Deformation of solids
• Etc.
Reversibility & Irreversibility: Crash Course Engineering #8 (11:04) 16
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Fall 2024 CHM 585 (Phys. Chem. 1):
Ch. 2

2.8 State Functions & Path Functions

↓ When ach
so

• ∆U is independent of the path connecting the i & f states,

and only depends on the i & f states.
• State Functions: Depend only on the state of the system
and not the path taken to reach the state:
f
U   dU  Uf  Ui
i
• In order for ∆U to depend only on the i & f states, the
value of the integral must be independent of the path. If
this is the case, U can be expressed as an infinitesimal
quantity, dU, that can be integrated. ↓ alway be can

• The quantity dU is called an exact differential. Integrated

• Cyclic integral: Applies to a cyclic path such that i=f. For U
or any other state function,
Britt
41

 dU  Uf  Uf  0 i
.....
& V
,
Tc 17
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17

2.8 State Functions & Path Functions

• Path Function: Depends on path/process/route
taken instead of only on the initial and final states.
• Demonstration that q & w are Path Functions:
no energet & = 0 then W = 0
in/out
↓ ↓

Av =0

-
T

about
compression go prwork
introduces E ,
so

w( + ) T
Not heating, only
dee to
due to compression

& path fet

State fet .

18

The AU sum
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doesn't change butEducation,
the Inc. /W will
All Rights Reserved
individual
,

18

Copyright 2023, Elizabeth A. Ploetz and

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Fall 2024 CHM 585 (Phys. Chem. 1):
Ch. 2

2.8 State Functions & Path Functions

• Properties of q & w:
• No↑exact differentials unless the path is specified.
I need to specify
• Incremental amounts are denoted dq and dw rather path
than “dq” and “dw,” to emphasize that incremental
initial
amounts of work are not exact differentials.
with &
d
don't
cant assign glo to
• There are no quantities ∆q, qf, qi, ∆w, wf, or wi. webe
& a a
sys >
-
g/w only
happen when there is
• Cannot refer to the w or q ‘possessed by’ the change to the sys a

Sys/Surr or the ‘change in’ w or q associated with a

process.
• If we say a process is isobaric, isochoric, isothermal,
or adiabatic, each of those are specifications of the
path (they are enough!). Then dq  dq; dw  dw.

19
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19

frite denestaa
↓2.9 Comparing Work for Rev. & Irrev. Processes
• Irreversible Scenario: Consider IG in a cylinder/piston
system with diathermal walls. State 1: T, Pext=P1, V1. Iso T
expansion by decreasing Pext to P2. State 2: T, Pext=P2, V2.
Iso T compression by increasing Pext to P1. What is ∆U, w, q dnew
for this cycle?
fixed
: Pext

D
↓
compress
②
AT O
=

② Du =0

P >Pz
③
,

< intend fin state are the same N2 > V ,

④ but w isn't

• P-V Diagram (a.k.a. “Indicator Diagram”):

w evaluated from area under/enclosed by curve.

20

20 ① ② Final

Copyright 2023, Elizabeth A. Ploetz and

Paul E. Smith 10
 ?
What makes something in rev/rew

Inew
: if

Rev :
allows sub of Pext = P

How can we expand then compress but it isn't reversible?

Fall 2024 CHM 585 (Phys. Chem. 1):
Ch. 2

2.9 Comparing Work for Rev. & Irrev. Processes

• Reversible Scenario: The same cyclical process is carried
out in a reversible cycle (P=Pext during the entire process; P
changes gradually during the expansion/compression& steps).does
anythingchar a
venal
?

• What is ∆U, w, q for this reversible isothermal cycle? when

Pressureisn't fixed ,
but it's eul
to
pressu inside o

0
Se ↑
=
AT =

as gers expands Pd
,

area under
cre : W

21
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21

①w -nRTen(t) 2(0 08314)

-

= .

What is the work done if 2.00 mol of IG undergoes

isothermal expansion starting from Pi = 25.0 bar & Vi =
4.50 L if the system goes through 3 different paths?
(1) Rev. expansion to Pf = 4.50 bar.
(2) 1-step irrev. expansion against Pext=4.50 bar to Pf=4.50 bar.
(3) 2-step irrev. expansion: 1st against Pext = 11.0 bar to Pint=11.0
bar. 2nd against Pext = 4.50 bar to Pf=4.50 bar.
Small

① w =
-n works for IG Rev .
expansion =
=
19 . 3k)

constant
② W = -
PextAV = -

Pext( Vi) - = 9 23k)

.

③ W =
-

PextDV - Vint Corresponds to Tint = -12 .

93k)

22
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Fall 2024 CHM 585 (Phys. Chem. 1):
Ch. 2

Cont’d

1) p
~
PiNi 2)
Pr
⑧
① drop to Pext

② expand

PfVf ①u
Work p : //////18
v >
IRREVERSIBLE
Reversible
ISTEP
Largest Area =
Largest W
3)p1 O
Pi Vi
,

Pint Vint
,

/00
,

! >
Pf Uf
,

>v
I RREVERSIBLE

2STEP

23
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23

2.9 Comparing Work for Rev. & Irrev. Processes

↓ increase # of steps
• In the limit that we
have many infinitely
small steps, we approach
magnitute
the reversible result.
↓ ↓ always
wak may dsys does

• |wrev| ≥ |wirrev| expan. Work

• wrev ≤ wirrev compress.

Max work that can be

extracted from a Sus
process is that obtained
under reversible
conditions.
• In real world, trade-
offs are made (other
factors to consider)!
24
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Fall 2024 CHM 585 (Phys. Chem. 1):
Ch. 2

2.10 Doing Work on the Sys and Changing the Sys

Energy from a Molecular Level Perspective more ? have to absod
up

• CM to QM. (classical quantum mechanics) equal to level next

vs .
↓ energy
• QM (PCII): In general, the energy levels of QM systems are
discrete (quantized) not continuous. Molecules can only
possess amounts of energy that correspond to these values.
• Stat. mech. (PCII): Relative probability of a molecule being
in a state corresponding to the allowed energy values ε1 & ε2 Molecules

at T is given by exp[-(ε2 - ε1)/kBT] N

in lu 2
Nad = lu l
-

,
hap depende
↑
a
Boltzman Distribution Law
vol of sys

Population a any level an e-F/RT

go from
low
LowT =
high energy level population to pop

E [depend
, on Volume U(V T)
,

Energy levels for a He atom confined to a 1D box.

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 25
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& more in low
energy

25

2.10 Doing Work on the Sys and Changing the Sys

Energy from a Molecular Level Perspective
• Heat: The energy levels are the same for different Ts, but
the populations shift. NO AV all energy leves stay thework = 0 so came

levels stay the same

levels ↑
O ↑ g & Pop in higher energy

O
Molecules absorb heat
O
and jump up an everyt
O Leve

10.0 nm box length at two diff. Ts

26
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Fall 2024 CHM 585 (Phys. Chem. 1):
Ch. 2

2.10 Doing Work on the Sys and Changing the Sys

Energy from a Molecular Level Perspective
• Work: Compression/expansion changes the energy levels
available to the system.
S

geb E(v) Vd DE4 (spacing)

bec AV = 0 Tr = Ti

constant v

a= 0 Tr = Ti
> >
-

After After
Initial
adiabatic isochoric
other cooling to
No
compression. 27
initial T.
every in <4)

↑ put
other than w
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27 energy
& then Tint is

in by cooled ti
compression to

so +↑ to

Tint

2.10 Doing Work on the Sys and Changing the Sys

Energy from a Molecular Level Perspective
• Work: Compression/expansion changes the energy levels
available to the system.
② ① vol of buy
changesIt 2

so the
enagy
levels change
(space shrinks

Two diff. box lengths at 0.20 K.

28
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Fall 2024 CHM 585 (Phys. Chem. 1):
Ch. 2

2.11 Heat Capacity

• Heat Capacity: Measure of energy required to change the

temperature of a substance by a given amount.
q dq Eq CdT
C  lim
=


T  0 T  T dT
f i

•Extensive (J/K). -
>
double sys ? = doubles in value

•Often defined on molar basis: Cm (J/K/mol).

•Specific heat capacity: C/mass.
•Molecules can’t store heat, despite the name! Could be
called ‘Energy Capacity.’
• Describes the thermal response of the system to heat flow.
• Can define heat capacity under different exp. conditions:
• Constant volume: C or C
a • Constant pressure:VC or V,m
>
- cont do to T &

charges pass
in work so all
goes any of

absorbed P C P,m O might go >

-
doing
work so some or to w

• CV ≠ CP. 29
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29

2.11 Heat Capacity

• CP,m given in Tables in Book:

• 2.3 Physical Properties of Selected Elements (298.15K)
• 2.4 Physical Properties of Selected Compounds (298.15K)
• 2.5 Gases in the Range 298-800K (T-dependent)
• 2.6 Solids (T-dependent)
• 4.1 Inorganic Compounds (298.15K)
• 4.2 Organic Compounds (298.15K)

30
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Fall 2024 CHM 585 (Phys. Chem. 1):
Ch. 2

all things a molecule can do

↓ D . F
. O

2.11 Heat Capacity Translation Vibration Rotation ,

Electronic

• Molecular Level Origins of Heat Capacity:

,
,

• Molecules can take up energy by translating faster,

rotating faster, vibrating faster, or becoming
electronically excited. => the you can store energy in those F D O
.
.
.

• E is gained/lost by a molecule through collisions with

other molecules. In a molecular collision, the amount of
energy than can be gained/lost is approx. kBT (order of
magnitude).

Order of Mag. Est.

kB= 1.381 x 10-23 J/K z

mut gep btun KF and vibration is too big

>
-

kBT @ 298K = 4.115 x 10-21 J 2 can't excite

KisT Rotation
RT @ 298K = 2.477 kJ/mol then we can
31-
> close
so not
he able
dump evage
you might
to tell
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31 a Room terry
work because the
require less
energy

2.11 Heat Capacity

• Molecular Level Origins of Heat Capacity:
• A given d.o.f. in a molecule can only take up energy through
collisions if ∆E  kBT.

Depiction of energy levels for each d.o.f. of a molecule:

grap size
> VJ R > T
E

·
· Want
· &

happen
under
normal T

kB= 1.381 x 10-23 J/K

kBT @ 298K = 4.115 x 10-21 J 32
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 Fall 2024 CHM 585 (Phys. Chem. 1):
Ch. 2

Remember

S
2.11 Heat Capacity
• Molecular Level Origins of Heat Capacity:
• ∆Eele >> ∆Evib >>N ∆Erot >> ∆Etrans
• Generally, molecules can be Trans and Rot excited by kBT
happen want man roomt

(∆E<kBT), but vibrations and electronic transitions are not

excited (in ground state) near R.T. (∆E>kBT).
Depiction of energy levels for each d.o.f. of a molecule:

kB= 1.381 x 10-23 J/K

-
kBT @ 298K = 4.115 x 10-21 J 33
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has enough thermal energy RT
33
collisions make them change in rotational Dof
to excite vibrations
Not high enough -
o eark = > need &T

LEARN & How do you apply this

2.11 Heat Capacity

NOTE : You need a band to
8 314.

lib and rotate C Mol .

K

• Molecular Level Origins of Heat Capacity: L

-

R =

• How much each d.o.f. contributes to CV,m? ↓ constan + 18 314)

• Each Trans: R/2

gas .

store y ineach can

.
D

• Each Rot: R/2 2 F depends or 3 rot D O . . on

Each Vib mode:

molecule
Shape (nonlinear has 3 like H20)
can't
stare
at
- • linear 2 H2

enco
YeRofPE • 1 R if ∆E/kT < 0.1
tap
Per vib D O F
room .

RaFIE
. .

+ & higher
[
↑
interacting
atoms are
• Partial R if 10 > ∆E/kT > 0.1
& lower T

• 0 R if ∆E/kT > 10. temp)

• Electronic: 0 for molecular (g)

& lowest + room

• Monatomics: Ne 3 (g)
Trans
only has d.o.f. trans be only are molecule

only, so CV,m=3R/2.
Can't vibrate or rotate -X , Y,z

Ar=(trans Ne or
h
• Diatomics: CO
---

=1 trans 31

ROT
↓
3
Z

RE

• Polyatomics: Higher values of CV,m

at Ts high enough to activate Vibs. 34
Copyright © 2019, 2013, 2010 Pearson Education, Inc. All Rights Reserved

34 DO F . .

N = #atoms
3N-5 for linear H20 (nonlinear)
3 N-6 for nonlinear 3(3) -
6 =
3 vib

Co

Copyright 2023, Elizabeth A. Ploetz and 5 1 vib

3(2) - =

Paul E. Smith 17
 Trans Rot Vib ToT Lunits R)
.

monatomic 3/2 X X 32
12 R in each direction YzkE + "212PE

diatomic 3/2 I 1/0 ? 5/2 + 0/1

If T ↓ then O

Linear Polyatomic 3/2 I

3N -
5/0 ? 5/2 + 3N 5/0 -

((02) ↑
vib Dof

Nonlinear Polyatomic 3/2 3/2 3N- 6/0 ? 3 + 3N -

6/8
Hz

-
F
0 - 0
H
- -

H
H -
H

3 atoms = 3 vibrations

E
① stretch bonds /sym stretch)
Depend on
:
bonds extend and compressa same time

-
& 470Y H

BAsym
04
stretch bonds expand back fat

H-0X
:
a
# -

H-H-& Ange opens and closea

Fall 2024 CHM 585 (Phys. Chem. 1):
Ch. 2

2.11 Heat Capacity

• Heat Capacity in Different Phases:
• (s): Collective Harmonic Oscillator Model of (s):
• (s)(l): Activates more low E modes 3D array of
• (l): 2 coupled springs.
• (l)(g): Local Vibs. in (l)  (g) Trans. ↓
small changes

• (g): Vib. modes of individual

molecules are activated
• CP, CV depend on T, but we Cl2
often assume it is independent
of T (reasonable over a small
T-interval).
• Ex: For water, CP is nearly
constant at the value of 4.18
J/g/K or 75.3 J/mol/K over
the range 0 - 100ºC.
35
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35

depends on how you heat it : No work sv

us = o

↓ Ci Cv

2.11 Heat Capacity ↓ cando

• Comparison of CV & CP:
• For Gases:
& DV
= 8

• CP > CV. Why? Wayst into VI So

& T
• V fixed: q flow into system, ∆U=q. Th
all gees heat
So

• P fixed: same q flow into system but it also expands

(w<0), so ∆U<q. Sys does work AU 9 +) adding
since = +
so we're
energ

• So, dTP < dTV for the same dq (heat flow).

• For IG: CP - CV = nR or CP,m - CV,m = R [Ch. 3]
• For solids and liquids: URSO
*
& so < p > Co divide by n
, so Cv , m = Cu molar
Wis small when heat Lig/sol

• CP ~ CV since V of (l) and (s) does not change much

>
-

with heating.
• Easier to measure CP rather than CV for (l) and (s).
So, CP,m is what is typically tabulated.

36
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36

Copyright 2023, Elizabeth A. Ploetz and

Paul E. Smith 18
Fall 2024 CHM 585 (Phys. Chem. 1):
Ch. 2

2.11 Heat Capacity

dq =
CdT

• Calculations: C =
d
capacity d a
e
bathweweknowheat
to
Isolated oil
water,
>
-
Sun

SYS

set

heat absorbed by any

heat
goesinS
constant
P TSys ,f TSurr ,f
at ↓

 
change Sys
to T
qP  C P
(T )dT   CPSurr (T )dT
TSys ,i TSurr ,i
TSys ,f
V
constant TSurr ,f

 
Sys
qV  C (T )dT   CVSurr (T )dT
↓

V
TSys ,i TSurr ,i

37
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37

The volume of a system consisting of an IG decreases

at constant pressure. As a result, the temperature of
↓ can do w

a 1.50 kg water bath (CP,water=4.18 J/g/K) in the

surroundings increases by 14.2 ºC. Calculate qP for the
system. = independent of T at

287 35K .

So we can
pull

glor
,
- out at

qp
= -

Curr dT don't know

***

Cp so

Tsurr i , use
Cpsum
sur r
=
-

Cp AT

- Cater AT

ap = -

89 0k).

& sys off 89 0k)

gave which
-

.
is

why Surr it

38
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38

Copyright 2023, Elizabeth A. Ploetz and

Paul E. Smith 19
Fall 2024 CHM 585 (Phys. Chem. 1):
Ch. 2

2.12 Determining ∆U & Introducing Enthalpy

Recall, U  q  w .
U  qV [Always] U  q [Constant V; no non-PV w]
• ∆U can be exp. determined by measuring the heat flow
between the Sys & Surr in a constant V process.
• Chem rxns are generally carried out under constant P rather
than constant V. Want an analog of ∆U for constant P.
• Derivation of the analog for constant P (Enthalpy, H):
① dU  dq  dw
 dqP  Pext dV  dqP  PdV [Constant P] >
-

 dU   dq   PdV
P

U  qP  P  V 
U  P  V   qP I doesn't
matter if its
or not
a ya
H  U  PV [New state function]
H  q [Constant P; no non-PV w]
39
H  qP [Always]
& heat absorbed
39
at constant &

2.13 q, w, ∆U, & ∆H Calcs for IG Processes

• An EoS is often needed, so system will generally be an IG.
• IG acts as a surrogate for more complex systems. Math is
simplified, so we can concentrate on the process.
• Further restrict to processes that don’t involve chm. rxn. or even in constant volume (C)
phase changes. ↓dependsen Ve
due to PV =
n12T

8
path ,
we can find DUIDH

• Generally, U(P,V,T). For IG, U(T) only, making H(T) only. So as long as
we know

• If know Ti, Tf, CV, CP, can calc ∆U and ∆H regardless of the * Twe c a n do it .

path for the IG: 2 why ?

U  qV   CV dT  CV T (if CV const.) [IG; No Chm

H  qP   CP dT  CP T (if CP const.) rxn or phase ∆]

• 1st Law links q, w, & ∆U. If any 2 of these quantities are

known; the 1st Law can be used to calc. the 3rd.
• Given the process, often possible to obtain the value of 1 or
more of q, w, ∆U, & ∆H without any calcs! 40
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40

Copyright 2023, Elizabeth A. Ploetz and

Paul E. Smith 20
 labe ? I
can only pick 2 to change
Why
u(V . Ti) U(V ,T2) A can't calculate
j Au exactly be it
-- - -...........

a Cp path
>
intermediate state
J depends
AV =
2v path
on

Cust but
ST = 0 ,

are
OCT) for 16 so intst .
might
Note : only energy in 16 sy = o be Cr
is KE if T is
, so same , the

energy is the same The

.
v U(V Tz) ,

volume doesn't .
matter

complexpansion under is othermal

T
break down into
Steps : I
parts
Olook for int : gU CuST (AH 15)
=
=
CAT can also be calculated only using

② go to final
stleg : then add leg I (red) +
leg = (green
Fall 2024 CHM 585 (Phys. Chem. 1):
Ch. 2

When considering q, w, ∆U, and ∆H for IG, what do we

know automatically just based on the types of
processes?

Isothermal process?
If 16 and AT = 0 then SU 0
q
=
= -w
AT =
0 substitute
- & fixed in closed So DurT 8
=
sys

AH = AV + DPV = AV + AnRT = su = 0

Adiabatic process?
9 = 0 V = w

a non-pu work
look
definition

Constant volume process where non-PV work is

impossible? ↑ No work on
gas

AV =
0 W = AV =
9

41
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41

monatomisolation
A 2.50 mol sample of an IG (CV,m = 3R/2) is subjected to
2 successive changes in state: (1) From 25.0 ºC and Ti
Di = 125103 Pa, the gas is expanded isothermally against a -T = 0

const. P of 15.2103 Pa to twice the initial volume. (2)

Then, the gas is cooled at const. V from 25.0 ºC to -29.0
ºC. Find q, w, ∆U, ∆H for each step & for the total
process.
① V
=
Vi = 2 vi

② IT = 0 SU = 0 SH = 0 q= w find w be
qu
neds AV=0 and wa don't have
that

W = -
SPextdv = -
PextAV =
-

753)

③ AV = 0 -w = 0 >
- AV =
q
WLO heat bath provides

S
doesn't depend on T

qu
↑ 9 , and

heat
gas expands

AV = qu = nCu moT = -1 . 68k] ve also

ST 0
so is
, =
turned into
su = 6
The V
q
1 .

changes
CH >
- AH =
nCp ,
mAT (Cpim
= Cr ,
m
+ R) but SU (v) is not
.
true
2 8)k)
42
-
=
H = SU + APV = AV + nRAT .

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42

Copyright 2023, Elizabeth A. Ploetz and

Paul E. Smith 21
 Fall 2024 CHM 585 (Phys. Chem. 1):
Ch. 2

Cont’d

D Ti Pi 125x10" Pa Pext 2x10' Pa Vf 2 Vi

°
25 C 15 DT 0 U 0 &H = 0 =
Vi 0 04 grit
q
= =
= =
.
= =
- 20 = .

273 15
SpextdV 2x/8P(ET) ((22
5(18 314(298
15) =
.

-
.

2x103 Pa
. .

= -
15
W 15 125x103
-
- =

298 15K
= .

.
.

W =
=
-

753 . 7) 9
=
753 75) AU = 0 &H = 0
.

When AV = 0 ,
Tis the only @DU = 0
+: = 298 . 15K
T1 = CK .
15K W = O Du =
gu

thing Au
affecting Du = n(v mdT = (2 . 5)(3 -
8 .
314/2)(244 .
15 -
295 . 15) = 1683 6) .

,
>
-

AU MRAT - 1683 6) + (2 5) (8 314) (C44 15 290 in)

DH ApV
-

AV = =
+ +
.
. .
= .
.

=
- 2805 94) .

Wi = 0 qz
= - 1683 6 .
DU
=
=
0 SHE = O

43
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43

A system containing 2.50 mol of an IG for which CV,m =

20.79 J/mol/K is taken through the cycle in the
following diagram. Calc q, w, ∆U, ∆H for each segment &
for the cycle assuming that heat capacity is independent
of T for the a.) forward and b.) reverse processes.
- Pext D=

① P = nRT = T O ·

== 79

Tz = 79 . 9 since 1- 3 is is othermal
AV =0

Tz = 2000K cooling at DV = 0 2- >

w = g

DT = 0
It 2 constant Pext
: expansion against
w = -

SPextdV = -
PextBV
·
DU =
nCv mAT - an 16 so we can use this
,

DH =
nCp mAT ,

AU , ->
g /technically ap so can use &H =
qp equation
above

39 8 k) 94 6k) SH =
qp
=
159k)
W = -
.
,
10 = .

44
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44

Copyright 2023, Elizabeth A. Ploetz and

Paul E. Smith 22
Fall 2024 CHM 585 (Phys. Chem. 1):
Ch. 2

Cont’d
Reu
2e 3 : Constant V cooling 31 : Isothermal compression

AT = 0 so DV =
DH = 0 q = w
0
Ar = 0 - w =

AU =
nCv mAT ,
=
qu =
-
99 .
6k) w = -

nRTen() = 5 35k
.

nCp mAT AU + APU -139k)

DH = or =
,

45
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45

Cont’d

Summary Table

46
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46

Copyright 2023, Elizabeth A. Ploetz and

Paul E. Smith 23
Fall 2024 CHM 585 (Phys. Chem. 1):
Ch. 2

2.50 mol of an IG with CV,m = 12.47 J/mol/K is expanded

adiabatically against a constant pressure of 1.00 bar. Ti=
325K, Pi=2.50 bar, Pf=1.25 bar. Calc Tf, q, w, ∆U, ∆H.
&

① a=0 Au = w
Vi
=
W SPextor F- PextBV

3
= -

W
AV =
Vf =
need f

AV nCv , mAT -

PextAV =
nCumST

1 78k) w
Pext (Vf-Vi)
-
=
Su
-
= .

96k)
DH DU + nIDT = -2
Pext
-
= .

TF 262k
ST(-)
=

Pext nCv mAT

-
.
=
.

47
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47

Cont’d

48
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48

Copyright 2023, Elizabeth A. Ploetz and

Paul E. Smith 24
Fall 2024 CHM 585 (Phys. Chem. 1):
Ch. 2

2.14 Reversible Adiabatic Expan./Compress. of IG

q0  U  w [Adiabatic]
dU  dw
dV
CV dT  Pext dV  nRT [Reversible, so P = Pext ]
V
dT dV
CV  nR
T V
f f
dT dV
i CV T  i nR V
Tf Vf
CV ln  nR ln [Constant CV ]
Ti Vi
Tf nR Vf
ln  ln
Ti CV Vi
 C  CV Vf
  P  ln [IG]
 C
 V  Vi p! "Ti = P !"T
T V
ln f      1  ln f
(Ef" (Y
[   CP / CV ]
Ti Vi
:

1 
Tf V  PV
 f   f f
Ti  Vi  Pi Vi
& 49
PV PV
a
 
i i
 f f Copyright © 2019, 2013, 2010 Pearson Education, Inc. All Rights Reserved

49

Calc. w if 1.25 mol of a monatomic IG is reversibly

adiabatically expanded from 320 K and Pi = 3.10 bar to Pf
= 1.00 bar.

50
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50

Copyright 2023, Elizabeth A. Ploetz and

Paul E. Smith 25
Fall 2024 CHM 585 (Phys. Chem. 1):
Ch. 2

Flow Chart Summary

w=- Pext dV
Irreversible Reversible IG

w  Pext V Fixed T Adiabatic

V2 T  V 
1 
Pf Vf
w  nRT ln f f
V1   
Ti  Vi  Pi Vi

PV
i i

 PV
f f


w  U  nCV ,m T

51
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51

Flow Chart Summary

U+PV
2 2
 PV
1 1

Fixed P
H=U+(PV) U+PV

 C dT  C dT
P V U+VP
CP const. CV const.

CP T CV T
U+(nRT)
IG Fixed n Fixed T (Ch. 4)
(CV  nR )T U+nR T U+RT  n

52
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52

Copyright 2023, Elizabeth A. Ploetz and

Paul E. Smith 26
Fall 2024 CHM 585 (Phys. Chem. 1):
Ch. 2

Recommended End of Chapter Problems:

4th Edition 8
Chapter 2
Problem (X=) 10
2 11
4 16
8 19
10 25
12 29
13 30
15 P 2.X 34
Q 2.X
16 35
17 36
18 38
19 39
22 46
23 48
24 49
52

Some of these are for practice, and some are the problems that will
appear as the online HW in Mastering Chemistry (MC). However, they may
have slight changes in the online HW, and the numbers may differ! 53
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53

Copyright 2023, Elizabeth A. Ploetz and

Paul E. Smith 27