Winter 2013 Chem 254: Introductory Thermodynamics

Chapter 3: The Math of Thermodynamics .................................................................................... 25

Derivatives of functions of a single variable ............................................................................. 25
Partial Derivatives ..................................................................................................................... 26
Total Differentials ..................................................................................................................... 28
Differential Forms ..................................................................................................................... 31
Integrals .................................................................................................................................... 32
Line Integrals ............................................................................................................................. 32
Exact vs Inexact Differential...................................................................................................... 33
Definition of and ................................................................................................................. 36
Dependence of U on T and V .................................................................................................... 37
Dependence of H on T and P .................................................................................................... 37
Derivations involving dH ........................................................................................................... 38
Relation between CP and CV (Exact) ......................................................................................... 39
Joule Thompson Experiment .................................................................................................... 39

Chapter 3: The Math of Thermodynamics

Derivatives of functions of a single variable

df f ( x h) f ( x )
lim
dx h 0 h instantaneous slope
f ( x h) f ( x h )
lim
h 0 2h

(better if done on a computer with finite step size)

Often used derivatives

df
f ( x)
dx
xa ax a 1
e ax aeax
1
ln(ax) x
ln(ax) ln a ln x

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sin(ax) a cos(ax)
cos(ax) a sin(ax)

Rules for Derivatives

d df dg
f ( x) g ( x)
dx dx dx
d df dg
f ( x) g ( x) g ( x) f ( x) Leibniz
dx dx dx
df df du
u ( x) Chain rule
dx du dx
d
Eg. sin( x 2 ) cos( x 2 )2 x
dx
d 2 x2 3 x
e2 x 3 x (4 x 3)
2
e
dx
df dg
g ( x) f ( x)
d f ( x) dx dx
Quotient Rule
dx g ( x) g ( x) 2

Partial Derivatives

f ( x, y) depends on multiple variables eg. T ( x, y, z ) the thermometer reading in a

room
f
Pronounced: di f , di x at constant y
x y
The change in function x -direction keeping y constant

Rules to take partial derivatives

same as in 1 dimension, treat remaining variable as constants

y2 x
f ( x, y) e x
2

f x2 y 2 x
e (2 x 1)
x y
f x2 y 2 x
e (2 y)
y x
f ( x, y) ln( x 2 2 xy)

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f 1
2 (2 x 2 y)
x y x 2 xy
f 1
2 (2 x)
y x x 2 xy

Higher Partial Derivatives

d 2 f ( x) d df
For one variable:
dx 2 dx dx
d2 d 1 2
Eg. ln( x 2 ) 2 2 x 2
dx 2
dx x x
2 f f
Partial derivatives: 2
x y x x y y
2 f f
2
y x y y x x

Mixed Derivatives
f f

x y x y y y y
x

f x2 2 xy
e x 2 xy (2 x 2 y )
2

e
x y
f x2 2 xy
e x 2 xy (2 x)
2

e
y x
f
(e )(2 x 2 y)
x 2 2 xy

y x y x y x
2 xy 2 xy
ex (2 x 2 y)(2 x) e x
2 2
(2)
f x2 2 xy
(e )(2 x)
x y x y x
2 xy 2 xy
ex (2 x 2 y)(2 x) e x
2 2
(2)
Order of derivatives does not matter
f 2 f 2 f

x y x y xy yx

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In mathematics
one would typically not write out whats kept constant
f f f f
instead of ; f ( x, y, z) instead of
x x y x x y , z

In Thermodynamics: ALWAYS write what is kept constant

V V
,
T P ,n T H

Total Differentials

when 2 or more variables are not constant

One dimension
df 1 d2 f 2 1 d3 f 3
df dx dx dx ....
dx 2! dx 2 3! dx3
df
dx for dx infinitesimal
dx

df
f ( x dx) f ( x)
dx x

Two dimensions
f f
df dx dy ....
x y y x
f ( x x, y y) f ( x, y)
f f
df x y
x y xy y x xy

x
in arbitrary direction , We can calculate the change in function f (for small x , y )
y

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Curve f ( x, y) 0

f f
df dx dy 0
x y y x
Calculate how much does y change if x x dx
f f

dy x y f f dx y x
dx dy
dx f x y y x dy f

y x x y
y 1
So keeping f constant
x f x

y f

Consider function f ( x, y, z ) 0 (surface in 3 dimensions)

f f
z constant : dx dy 0
x y , z y z , x
f

x y z ,. x
f
y z

x z , y
f f
y constant: dx dz 0
x y , z z y , x
f

z x z ,. y
f
x y

z x , y
f f
x constant: dy dz 0
y x , z z x , y

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f

y z x ,. y

z x f

y z , x
x z y
Cyclic Rule 1 for f ( x, y, z ) 0
y z x y z x

Proof:
f f f
1
3

x z y y x , z x y , z z x , y
1
y z x y z x f f f

x z , y z x , y y z , x
From the cyclic rule
y z 1 y

z x x y x x z
y
z
Way to remember cyclic rule
z z y

x y y x x z

Application in Thermodynamics
nRT n2
Van der Waals P a 2 nRT (V nb)1 an2V 2
V nb V
P nR

T V V nb
P
nRT (1)(V nb) an (2)V
2 2 3

V T
V V
: first derive V f ( P, T ) then find (very hard)
P T P T

V
How do we calculate ?
P T

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V 1
We can use P
P T

V T
V V P
(1) (cyclic rule)
T P P T T V
P P
Calculate using above results
T V V T

Differential Forms

General differential form (Pfaff): df g ( x, y)dx h( x, y)dy

f f
Question: Is there a function F ( x, y) such that g ( x, y ) and h( x, y ) ?
x y y x
df dF Path
df Ffinal Finitial
If F ( x, y) associated with g ( x, y)dx h( x, y)dy then:

y g ( x, y) x h( x, y)
x y
If this relationship holds: a function F ( x, y) does exist
If this relationship does not hold: F ( x, y) does not exist

df g ( x, y)dx h( x, y)dy is an exact differential if and only if

y g ( x, y) x h( x, y) , otherwise its an inexact differential
x y

If df is an exact differential Path

df Ffinal Finitial
independent of path that runs between initial and final state

dU , dH , dS , dG, dA : exact differential

q, w : inexact differential

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Integrals

n
f ( x)dx lim f ( x1 )dx (Area under function)
b
a x 0
i 1

f ( xi )x = area for each rectangle

dF b
Find function F ( x) such that
dx
f ( x) then: a
f ( x)dx F (b) F (a)

Strategy for solving integrals

1) - guess solution,
dF
- verify the differentiation f ( x) ?
dx
- if not right tinker with constants
2) - Look them up (books) or use math programs
Examples in thermodynamics
dF
f ( x) F ( x)
dx
1 a 1 1
x a (a 1) x (a 1) xa xa
a 1 (a 1)
b b
b ln x ln xb
x x
1 ax 1 ax
e ax e ae
a a

Line Integrals

Consider differential df g ( x, y)dx h( x, y)dy consider paths

y( x) P1 ( x) and y( x) P2 ( x)

P1 ( x )
df I1 P2 ( x )
df I 2 in general I1 I 2

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dP1
y( x) P1 ( x) dy dx
dx
I1
Path
g ( x, y)dx h( x, y)dy df
x2 dP
I1 g x, P1 ( x) dx h x, P1 ( x) 1 dx
x1
dx
x2 dP
I1 g x, P1 ( x) h x, P1 ( x) 1 dx
x1
dx
x2
I1 c( x)dx reduced to 1d integral
x1

Likewise:
x2 dP
I 2 g x, P2 ( x) h x, P2 ( x) 2 dx
x1
dx
integrals are different
But: they are the same if and only df is an exact differential
If df exact differential then I1 I ( x, y) final I ( x, y)initial

Exact vs Inexact Differential

d d
Inexact differential: g ( x, y ) h( x, y )
dy x dx y

Path
df gives results but depends on path

Real life example of exact differential: height differences on a mountain

It is clear the height difference is independent of how

you get there

How do you get contours for map? Measure the height differences between
neighbouring points
dh hx dx hy dy measure in small steps
h( x, y) defines height function of x, y

Real life example of Inexact differential: shoveling snow

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dsnow d x dx d y dy
The amount of snow you shovel depends on
the path you take between points A and B
Exact differential:
df 2 xydx x 2 dy

(2 xy ) x ( x 2 ) y
y x
2 x 2 x Therefore, is exact differential

df is independent of path

dF dF
F ( x) such that 2 xy ; x F ( x, y) x y
2 2

dx y dy x

dP1 d ( y x)
P1 ( x) : y x 1
dx dx
dP2 d ( y x 2 )
P2 ( x) : y x 2 2x
dx dx

I1 g ( x, y)dx h( x, y)dy
Path

x 1 dP1
g x, P1 ( x) dx h x, P1 ( x) dx
x 0 dx
1 1
I1 2 x xdx x 2 1dx 3x 2 dx
0 0

3 1
x 1
0
1 1
I 2 2 x x 2 dx x 2 2 xdx 4 x3 dx
0 0

4 1
x 1 (integral result is the same because exact differential)
0

F ( x, y) x 2 y I n F (1,1) F (0,0) 1 0 1

Example of inexact differential:

df x 2 dx 2 xydy P1 ( x) : y x ; P2 ( x) : y x 2

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1 1
I1 x 2 1dx 2 x x 1dx 3x 2 dx
0 0

3 1
x 1
0
1 1
I 2 x 2 dx 2 x x 2 2 xdx x 2 4 x 4 dx
0 0
1
1 3 4 5 1 4 17
x x 1
3 5 0 3 5 15

2
( x ) x (2 xy) y ?
y x
0 2y not equal, differential is not exact, I1 I 2 in general

F F
x and 2 xy ?
2
Does F ( x, y) exist such that
x y y x
F 1 3
x F x c
2

x y 3
F
2 xy F xy 2 c Not equal
y x

Hence: for inexact differentials, line integrals can be calculated, but results depends on
path. True for q, w in thermo or shoveling snow!

Summary of rules from math

y 1 y y z

x z x x z z x x y

y z
Exact differential: df g ( x, y)dx h( x, y)dy

y g ( x, y ) x f ( x, y )
x y

Path
df is independent of path

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Back to Thermodynamics!

Definition of and

1 V
Define: in units K 0 usually
-1
V T P
V
V : Volumetric thermal Expansion coefficient
T P
1 V
in Bar
-1
0
V P T
V
V : Isothermal compressibility
P T

For solids and liquids and are more or less constant

For gases and are not constant

nRT
Ideal gas: V
P
1 V nR P 1

V T P P nRT T
1 V nRT P 1
( ) 2
V P T P nRT P
P 1 1
V
V T V

P T
V

P P V T P V
V
T V V T T P V

P T
P
hard to measure obtain as
T V
P P
dP dT dV
T V V T

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1 dV
dT
V
f f 1 f dV
Path dP i dT i V
1 Vf
P T ln
Vi
Vf
ln T P
Vi

Dependence of U on T and V

U U
dU dT dV
T V V T
dU q w : inexact differential
q Pext dV assume constant volume
dU q qV CV dT
U CV T if V constant
U
lim
T 0 T
CV
V
U
CV
T V

U P
T P T P (will be derived later)
V T T

Dependence of H on T and P

H for constant pressure H qP CP T

H H
lim CP
T P T P
T 0

H H V
CP T V V (1 T )
T P P T T P
(to be derived later too)

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For Ideal gases

1 1
;
T P As expected
U P P
T P T P 0
V T T T
H V 1
T V V (1 T ) 0
P T T P T

Derivations involving dH

dH dU d ( PV )
dH dU VdP PdV
H H U U
dT dP dT dV VdP PdV
T P P T T V V T
H U
CP dT V dP CV dT P dV
P T V T
U P
Use P T (relation stated before)
V T T V
H P
CP dT V dP CV dT T dV
P T T V
assume T is constant (some process)
H P
P V dP T T dV ( T constant)
T V
H P V
V lim T
P T P 0
T V P T
H P V
V T now use cyclic rule
P T T V P T
H V
V T
P T T P

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Relation between CP and CV (Exact)

H U
CP dT V dP CV dT P dV
P T V T
Assume P constant
P V
CP CV T
T V T P

CP CV T V

2
CP CV TV (exact)

For ideal gas
P V
CP CV T
T V T P
P nRT nR V nRT nR
;
T V T V V V T P T P P P
nR nR nRT
CP CV T CV nR
V P PV
CP CV nR (used and derived before)

Joule Thompson Experiment

T
CJT (Joule Thompson Coefficient, definition)
P H
H H T
CP CJT
P T T P P H

P1 P2 qtotal 0 qI qII
H is constant during process

If H is constant:

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T T T
lim 2 1 CJT
P2 P1 P P
2 1 H P H
H
CP CJT V VT
P T
1 V
CP CJT measures
V T P
CJT 0 for ideal gases

Utotal U I U II w P1V1 P2 V2 q0
U I P1V1 U II P2V2 0

Since P1 and P2 are kept constant:

Htotal H I H II 0
H total is a constant

Joule-Thompson measurement in practice

Apply P1 P2 , T1 then measure T2 CJT

CJT as a function of T , P

Chapter 3: The Math of ThermodynamicsChapter 3: The Math of Thermodynamics 40