2.

The First Law

Thermodynamics
equilibrium thermodynamics
characterize equilibrium states
which equilibrium states can be reached from a
given initial state (i or 1): allowed processes
which processes occur spontaneously
system
PChem I 2.1
isolated: no interaction at all with surroundings
example: Dewar ask with absolutely rigid walls in a
Faraday cage on the space station
idealization, but useful
closed: exchange of energy, no exchange of matter
example: photochemical batch reactor
open: exchange of matter and energy
example: living systems
work: one way to interact with system
Work is done if the process could be used to bring
about a change in the height of a weight somewhere
in the surroundings.
PChem I 2.2
work is done by the system if the weight is raised
work is done on the system if the weight is lowered
PChem I 2.3
sign convention: viewpoint of the system
w positive, if work is done on the system
w negative, if work is done by the system
mechanics: w =

d; if

F||

d: w =Fd
expansion/compression of a uid
P
ex
P
ex
P, V P dP,
V +dV
_
dx
P =
F
A
expansion: external force F =P
ex
A
dw =P
ex
A dx =P
ex
dV
minus sign: according to sign convention dw must
PChem I 2.4
be negative, since work is done by the system during
expansion
compression: the same formula applies
dw =P
ex
dV
since dV < 0, we have dw > 0, as it should be, since
work is done on the system during compression
expansion/compression work (or volume-pressure
work):
w =
_
V
2
V
1
P
ex
dV general
energy: capacity to do work
energy increased if w >0, decreased if w <0
experiments show that energy can also be increased
by heating
diathermic wall: heat ow possible
PChem I 2.5
adiabatic wall: no change in energy if no work can be
done; no heat ow possible
First Law of Thermodynamics
The work needed to change an adiabatic system from
one specied state to another specied state is the
same however the work is done.
for example: mechanical work, electrical work, mag-
netic work
w
ad,1
=w
ad,2
=w
ad,3
=w
ad,4
=. . . =w
ad
(i , f )
Adiabatic work does not depend on the path, but only
PChem I 2.6
on the initial state i and the nal state f .
U
f
U
i
w
ad
(i , f )
U = internal energy, state function
can measure only U =U
f
U
i
replace adiabatic walls by diathermic walls
work is now path-dependent
mechanical denition of heat:
q U w =w
ad
w
First Law:
(1) There exists a state function U, the internal ener-
gy, for the system.
(2) If the state of the system changes, then
U =q +w
PChem I 2.7
U =q +w conservation of energy
6 6 6
state function path function
? ?
what crosses the boundary
rst law =U =const for an isolated system
to make the rst law operational, consider innitesi-
mal changes
dU =dq +dw
PV T systems:
w =
_
V
f
V
i
P
ex
dV
1. expansion into vacuum = free expansion, P
ex
= 0,
no weight raised or lowered
w =0J
PChem I 2.8
2. expansion against constant external pressure
w =
_
V
f
V
i
P
ex
dV =P
ex
_
V
f
V
i
dV =P
ex
(V
f
V
i
)
w =P
ex
V
reversible change (process): change that can be re-
versed, i.e., undone, by an innitesimal modication
of a variable
system is in equilibrium with its surroundings
reversible paths lie entirely in the surface of equilibri-
um states
reversible processes are quasistatic
3. isothermal reversible expansion:
expansion P
ex
<P: reversible P
ex
=P dP
compression P
ex
>P: reversible P
ex
=P +dP
PChem I 2.9
change from expansion to compression or vice versa:
2dP
dw
rev
=P
ex
dV =(P dP)dV
dw
rev
=PdV dPdV
dw
rev
=PdV reversible process
w
rev
=
_
V
f
V
i
PdV
need equation of state P =P(V, T)!
isothermal, reversible expansion of an ideal gas;
closed system n =const
w
rev
=
_
V
f
V
i
PdV =
_
V
f
V
i
nRT
V
dV =nRT
_
V
f
V
i
1
V
dV
=nRT [lnV ]
V
f
V
i
=nRT(lnV
f
lnV
i
)
PChem I 2.10
w
rev
=nRT ln
_
V
f
V
i
_
ideal gas, isothermal, reversible
since P
f
V
f
= P
i
V
i
for ideal gas and isothermal, we
have the equivalent form
w
rev
=nRT ln
_
P
i
P
f
_
ideal gas, isothermal, reversible
indicator diagram
isothermal, reversible: w =///
constant external pressure: w =\\\
PChem I 2.11
How do we measure U?
dU =dq +dw
exp
+dw
e
where dw
exp
is expansion work and dw
e
is extra
work, i.e., work in addition to expansion work, e.g.,
electrical work.
Consider a constant-volume process (isochoric pro-
cess). Then dw
exp
= 0. Assume further that no other
kind of work is possible, i.e., dw
e
=0. Then
dU =dq
V
or
U =q
V
In general
dq =C(T)dT
where C(T) is the heat capacity, an extensive quan-
tity. Since q is a path function, the heat capacity C
PChem I 2.12
depends on the type of process or change that oc-
curs. If C(T) = const is a good approximation for the
range of temperatures involved in the process, then
q =CT
For an isochoric process,
dq
V
=C
V
dT
where C
V
(T) is the heat capacity at constant volume.
For a constant-pressure process (isobaric process)
dq
P
=C
P
(T)dT
where C
P
(T) is the heat capacity at constant pres-
sure. Generally C
P
>C
V
, except if the uid contracts
upon heating, e.g., water in the range 0

C 4

C at
1 atm.
relation between C
V
and C
P
(for a derivation, see Further
Information 1 on page 2.36)
C
P
C
V
=

2
V T

T
PChem I 2.13
where

1
V
_
V
T
_
P
isobaric thermal expansivity

T

1
V
_
V
P
_
T
isothermal compressibility
For ideal gases, the relation reduces to
C
P
C
V
=nR
For a constant-volume process,
dU =C
V
dT
Considering U to be a function of T and V , U =
U(T, V ), then
C
V
=
dU
dT
for V =const
More rigorously,
C
V
=
_
U
T
_
V
PChem I 2.14
Use constant-volume bomb calorimeter to measure
U:
U =
_
f
i
dq
V
=
_
f
i
C
V
(T)dT
If C
V
(T) =C
V
=const is a good approximation for the
range of temperatures involved in the process, then
U =q
V
=C
V
T for isochoric processes
reactions typically occur at P =const
dU =dq +dw
exp
if dw
e
=0
since dw
exp
<0, we have
dU <dq
P
some heat was used by the system to do expansion
work!
PChem I 2.15
new state function
H =U +PV enthalpy
dH =dU +d(PV )
=dU +V dP +PdV
=dq +dw+V dP +PdV (dw =dw
exp
+dw
e
)
=dq PdV +dw
e
+V dP +PdV
=dq +V dP +dw
e
(Since H is a state function, it is no restriction of gen-
erality that we have used dw
exp
=dw
rev
=PdV .)
For a constant-pressure process and no extra work
dH =dq
P
Considering H to be a function of T and P, H =
H(T, P), then
C
P
=
dH
dT
for P =const
PChem I 2.16
More rigorously,
C
P
=
_
H
T
_
P
H =
_
f
i
C
P
(T)dT for P =const
If C
P
(T) =C
P
= const is a good approximation for the
range of temperatures involved in the process, then
H =q
P
=C
P
T for isobaric processes
If it is necessary to take into account the variation
of the heat capacity with temperature, the following
approximate empirical expression is commonly used:
C
P
(T) =a +bT +
c
T
2
where a, b and c are empirical parameters that are
independent of T and are tabulated for various sub-
stances.
PChem I 2.17
With this form
H = H(T
2
) H(T
1
) =a(T
2
T
1
) +
1
2
b(T
2
2
T
2
1
)
c
_
1
T
2

1
T
1
_
P =const
Note:
H =U +(PV )
=U +P
f
V
f
P
i
V
i
For an ideal gas, PV =nRT: H =U +(nRT), and
if n =const, i.e., closed system, H =U +nRT
thermochemistry
endothermic process exothermic process
(a) container with adiabatic walls:
endothermic: T decreases
exothermic: T increases
PChem I 2.18
(b) container with diathermic walls; isothermal pro-
cess
endothermic: q positive
exothermic: q negative
[Figure: endo- and exothermic processes, Fig. 2-2]
most chemical reactions take place at constant pres-
sure: enthalpy changes H
frequently reported for a set of standard conditions
standard enthalpy changes H

standard state
The standard state of a substance at a specied tem-
perature is its pure form at that temperature and a
pressure of 1 bar. (P

=1bar)
Remarks: (1) older values (pre-1982) use P

=1atm
(2) for real gases the nonideality is removed, discussed later
conventional temperature: 298.15K
phase = a specic state of matter that is uniform
throughout in composition and physical state
PChem I 2.19
phase transition: conversion of one phase of a sub-
stance, say a to another phase, say b, at constant
pressure

trs
H = H
b
H
a
=q
P
enthalpy of transition
examples: enthalpy of vaporization, enthalpy of fu-
sion, enthalpy of sublimation, . . .

trs
H >0 from more ordered to less ordered phases
standard enthalpy of vaporization; example
H
2
O(l) H
2
O(g)
vap
H

(373K) =+40.66kJ mol

1
H
2
O(l) H
2
O(g)
vap
H

(298K) =+44kJ mol

1
standard enthalpy of fusion; example
H
2
O(s) H
2
O(l)
fus
H

(273K) =+6.01kJ mol

1
sublimation: solid vapor; reverse: vapor deposition
s g =s l + l g
PChem I 2.20

sub
H

=
fus
H

+
vap
H

standard enthalpy of solution, enthalpy of ionization,

. . . , bond dissociation enthalpy
standard reaction enthalpy; example
CH
4
(g)+2O
2
(g) CO
2
(g)+2H
2
O(l)
r
H

=890kJ mol
1
thermochemical equation
can be written as

r
H

= H

(CO
2
(g))+2H

(H
2
O(l))H

(CH
4
(g))2H

(O
2
(g))
or in general

r
H

products

prod.
H

(prod.)

reactants

react.
H

(react.)
H > 0 endothermic reaction, H < 0 exothermic re-
action
PChem I 2.21
enthalpy is a state function =Hesss Law:
If a process occurs in stages or steps (all at the same
temperature and pressure), even if only hypothetical-
ly, the enthalpy change for the overall reaction (net
process) is the sum of the enthalpy changes for the
individual steps.
example:
2C(s) +2O
2
(g) 2CO
2
(g) H =?
2C(s) +O
2
(g) 2CO(g) H =221.0kJ/mol
2CO(g) +O
2
(g) 2CO
2
(g) H =566.0kJ/mol
2C(s) +2O
2
(g) 2CO
2
(g) H =787.0kJ/mol
standard enthalpy of formation
f
H

= standard
reaction enthalpy for the formation of the compound
from its elements in their references states
reference state = most stable form at the specied
temperature and P

PChem I 2.22
the standard enthalpy of formation of each element
in its reference state is zero

r
H

products

prod.

f
H

(prod.)

reactants

react.

f
H

(react.)
How do we obtain H at temperatures different from
the conventional temperature?
H increases with increasing temperature
H(T
2
) = H(T
1
) +
_
T
2
T
1
C
P
(T)dT P =const
applies to each species in a reaction, thus

r
H

(T
2
) =
r
H

(T
1
) +
_
T
2
T
1
C
P
(T)dT P =const
where
C
P
(T) =

products

prod.
C
P
(prod.)

reactants

react.
C
P
(react.)
PChem I 2.23
Kirchhoffs Law
for moderate changes in temperature C
P
(T) C
P
and
C
P
(T) C
P
; otherwise use C
P
(T) =a +bT +c/T
2
state function: U, H, P, . . .
U =
_
f
i
dU =U
f
U
i
path function: w, q
q =
_
f
i ;path
dq (=q
f
q
i
!!!!)
dU exact differential; dq inexact differential
state function exact differential
PVT system
U(P, V, T), equation of state F(P, V, T) =0
U(T, V ) or U(T, P) or U(V, P)
PChem I 2.24
most convenient choice: U(T, V )
(T, V ) (T +dT, V +dV ) :
U(T, V ) U(T +dT, V +dV ) =U +dU
dU =
_
U
T
_
V
dT +
_
U
V
_
T
dV
general function f (x, y)
differential: d f =
_
f
x
_
y
dx +
_
f
y
_
x
dy
physical meaning of partial derivatives:
dU =C
V
dT +
T
dV

T

_
U
V
_
T
internal pressure
response of internal energy U to changes in temper-
ature T for V =const: C
V
=
_
U
T
_
V
[Figure: Fig. 2-22]
response of internal energy U to changes in volume
V for T =const:
T
=
_
U
V
_
T
[Figure: Fig. 2-24]
what is
T
?
PChem I 2.25
ideal gas: Joule experiment
[Figure: Joule experiment, Fig. 2-26]
i : gas in left compartment, V
i
; right compartment
vacuum; temperature T
i
f : gas in both compartments: V
f
, T
f
experiment: T
f
=T
i
U =q+w; w =0, free expansion; q =0, since T
f
=T
i
and C = =U =0
for ideal gas U(T, V ) =U(T)
for ideal gas
T
=
_
U
V
_
T
=0
for ideal gas U =C
V
T
This holds for all changes for an ideal gas; V need not
be constant!
ideal gas: isothermal isoergic !!
ideal gas in the strict sense: C
V
(T) =C
V
PChem I 2.26

T
for real gases [Figure: Fig. 2-25]
ideal gas: H =U +PV =U(T) +nRT = H = H(T)
H =U +(PV ) =U +(nRT)
n =const: H =C
V
T +nRT =(C
V
+nR)T
for ideal gas H =C
P
T
This holds for all changes for an ideal gas; P need not
be constant!
ideal gas: isothermal isenthalpic !!
test for exact differential
d f =
_
f
x
_
y
dx +
_
f
y
_
x
dy
is exact, if and only if

2
f
yx
=

2
f
xy
PChem I 2.27
state function exact differential
mixed second derivatives are equal
U is a state function

2
U
V T
=

2
U
TV
C
V
V
=

T
T
for ideal gas: C
V
=const and
T
=0 =
C
V
V
=0 =

T
T

we know that
_
U
T
_
V
=C
V
what about
_
U
T
_
P
?
changing the independent variables from (T, V ) to
(T, P), i.e., considering U(T, P) instead of U(T, V ), one
obtains (for a derivation, see Further Information 2 on page
2.37)
_
U
T
_
P
=C
V
+
T
_
V
T
_
P
PChem I 2.28
_
U
T
_
P
=C
V
+
T
V
thermodynamic relation, universally valid
special case: ideal gas
T
=0
_
U
T
_
P
=C
V
state function enthalpy H; consider to be a function
of T and P
H = H(T, P)
dH =
_
H
T
_
P
dT +
_
H
P
_
T
dP
dH =C
P
dT +
_
H
P
_
T
dP

T

_
H
P
_
T
isothermal Joule-Thomson coefcient
dH =C
P
dT +
T
dP
relations for partial derivatives:
_
y
x
_
z
=
1
_
x
y
_
z
(1)
PChem I 2.29
_
x
y
_
z
=
_
x
z
_
y
_
z
y
_
x
(2)
Using relation (2):
_
H
P
_
T
=
_
H
T
_
P
_
T
P
_
H
_
H
P
_
T
=C
P
_
T
P
_
H

_
T
P
_
H
Joule-Thomson coefcient

T
=C
P

dH =C
P
dT C
P
dP
_
T
P
_
H
==
_
<0 if T >0 for P <0
>0 if T <0 for P <0
ideal gas: H(T, P) = H(T) =
T
=
_
H
P
_
T
=0 ==0
example of a constant enthalpy process: push gas
in an adiabatic container through a throttle (porous
PChem I 2.30
plug); i = high pressure side, f = low pressure side;
xed amount of gas
[Figure: throttling experiment, Fig. 2-28]
U =q +w
U =w
w =w
1
+w
2
w
1
=P
i
(0V
i
) =P
i
V
i
w
2
=P
f
(V
f
0) =P
f
V
f
U =U
f
U
i
=w =P
i
V
i
P
f
V
f
U
f
+P
f
V
f
=U
i
+P
i
V
i
H
f
= H
i
usually is measured by measuring
T
: pump gas
through a heat exchanger (ensure T =const), through
a porous plug inside a thermally insulated container,
then through a heater to offset the cooling; measure
P and H = heat provided by heater:
T
=H/P
as P 0
PChem I 2.31
[Figure: Joule-Thomson expansion, Fig. 2-30 ]
<0
inversion temperature T
I
>0
[Figure: Joule-Thomson coefcient, Fig. 2-31 & 2-32]
changing the independent variables for the enthalpy
H from (T, P) to (T, V ), we obtain (see Further Information
3 on page 2.38)
_
H
T
_
V
=
_
1

T
_
C
P
adiabatic expansion/compression
dU =dq +dw
adiabatic process dq =0: dU =dw
ideal gas for the remainder:
dU =C
V
dT (for all processes in an ideal gas)
w
ad
=
_
f
i
C
V
dT =C
V
T
PChem I 2.32
(1) xed external pressure
w =P
ex
V (general)
P
ex
V =C
V
T
T =
P
ex
V
C
V
T
f
T
i
=
P
ex
(V
f
V
i
)
C
V
=
P
ex
_
nRT
f
P
f

nRT
i
P
i
_
C
V
(2) reversible
dw =PdV (general)
dw
ad
=C
V
dT
C
V
dT =PdV reversible, adiabatic, ideal gas
P =
nRT
V
C
V
dT =
nRT
V
dV
C
V
T
dT =
nR
V
dV
PChem I 2.33
_
T
f
T
i
C
V
T
dT =
_
V
f
V
i
nR
V
dV
C
V
ln
_
T
f
T
i
_
=nRln
_
V
f
V
i
_
ln
_
T
f
T
i
_
=
nR
C
V
ln
_
V
f
V
i
_
=
nR
C
V
ln
_
V
i
V
f
_
c
C
V
nR
T
f
T
i
=
_
V
i
V
f
_
1/c
T
f
V
1/c
f
=T
i
V
1/c
i
or TV
1/c
=const
1
c
=
nR
C
V
=
C
P
C
V
C
V
=
C
P
C
V
1

C
P
C
V
TV
1
=const adiabats
PV =nRT
PV

=const adiabats
PChem I 2.34
compare to isotherms PV =const [Figure: Fig. 2-18b]
third form of the adiabats: TV
1
= const and the
equation of state PV =nRT yield
T
_
nRT
P
_
1
=const
T
T
1
P
1
=
const
(nR)
1
T

P
+1
=const
T P
1+
1

=const adiabats
caution: the adiabats can only be used for reversible
adiabatic processes in an ideal gas!!
PChem I 2.35
Further Information 1:
C
P
C
V
=
_
H
T
_
P

_
U
T
_
V
=
_
(U +PV )
T
_
P

_
U
T
_
V
=
_
U
T
_
P
+
_
PV
T
_
P

_
U
T
_
V
= C
V
+
T
V +P
_
V
T
_
P
C
V
=
T
V +PV
C
P
C
V
=V (
T
+P)
prove later (2nd law) that
_
U
V
_
T
=
T
=T
_
P
T
_
V
P
so
C
P
C
V
=V T
_
P
T
_
V
_
P
T
_
V
=
_
P
V
_
T
_
V
T
_
P
Eq. (2)
PChem I 2.36
_
P
T
_
V
=
_
P
V
_
T
V
_
P
T
_
V
=
V
_
V
P
_
T
Eq. (1)
_
P
T
_
V
=
V
V
T
=

T
Further Information 2:
dV =
_
V
T
_
P
dT +
_
V
P
_
T
dP
dU =C
V
dT +
T
dV
dU =C
V
dT +
T
__
V
T
_
P
dT +
_
V
P
_
T
dP
_
dU =
_
C
V
+
T
_
V
T
_
P
_
dT +
T
_
V
P
_
T
dP
dU =
_
U
T
_
P
dT +
_
U
P
_
T
dP
compare coefcients
PChem I 2.37
_
U
T
_
P
=C
V
+
T
_
V
T
_
P
_
U
T
_
P
=C
V
+
T
V
Further Information 3
dH =
_
H
T
_
P
dT +
_
H
P
_
T
dP
=C
P
dT +
_
H
P
_
T
dP
P =P(T, V )
dH =C
p
dT +
_
H
P
_
T
__
P
T
_
V
dT +
_
P
V
_
T
dV
_
dH =
_
C
p
+
_
H
P
_
T
_
P
T
_
V
_
dT +
_
H
P
_
T
_
P
V
_
T
dV
_
H
T
_
V
=C
P
+
_
H
P
_
T
_
P
T
_
V
_
H
T
_
V
=C
P
C
P

T
PChem I 2.38
_
H
T
_
V
=
_
1

T
_
C
P
PChem I 2.39