UNIVERSITY OF WITSWATERSAND

Thermodynamics Assignment 1
VASSILI REVELAS

715336

Question 1

Z =X 2 Y 2

(a) Given:

X YZ
Y

Z 2 Y 2

(rearrange equation Z to make X subject of equation and

differentiate with respect to Y)

ZX

Y
Z

1
Z
2
X

1
2

(rearrange equation Z to make Y subject of equation and

differentiate with respect to Z)

(b) The following expression is used to develop triple product:

(c) Through direct substitution the following relationship can be shown:

YX

Z
Z
Y
=
YZ
X
X
Y

XY

Z XY
Y ZX
X
X YZ
Z
=1
Y

Using the Triple product:

Z XY
Z YX
X YZ Z 2
=2 X Y 2 ,
=X 2 2Y ,
= 2
X
Y
Y
Y

Substitute the following terms:

Y 1 Z 2
2
2X
Z 2 Y =1
2
X
Rearrange the equation:

2 X Y 2=

YX

1
2

(2 Z X )

(Z

1
2

Z
XY
Z
Y
=
X
X YZ
Y

(in the form:

Simplifying the right hand side of the equation gives:

2X

Y2

=2X

Y2

to get:

YX

Z
XY
Z
Y
=
X
X YZ
Y

Both sides are equal therefore, proving the relationship (

) is true.

(2a) Using Legendre Transformation methods, the following three equations were
formed from the following equation: dU=TdS-PdV
(i)

The Legendre Transformation rule is described as: F=YTherefore, the equation dU=TdS-Pdv
By definition: A=U-TS
dA=dU-TdS-SdT
dA=TdS-PdV-SdT-TdS
Simplifying the equation gives :
d

A TV

=-PdV-SdT

(ii)

F2=Y-

C2 X 2

By definition:H=U+PV
dH=dU+PdV+VdP
dH=TdS-PdV+PdV+VdP

d H SP=TdS+VdP

(iii)

F3= Y-

C1 X 1

C2 X 2

By definition :G=U+PV-TS
dG=dU+VdP+PdV-TdS-SdT
dG=TdS-PdV+VdP+PdV-TdS-SdT
d

(b)

GTP =VdPSdT

Show:
d

U sv
S

=T

SV

U =TdSPdV
d U SV
dV
=T P
dS
dS

Placing the following restrictions: dV=0,dS0 we get :

U sv
S

=T

C1 X 1

SV

U
=P
V

Show:

U SV =TdSPdV

SV

dU
dS
=T
P
dV
dV
Place the following restrictions: dS=0,dV0 we get :
SV

U
=P
V
SP

Show:
d

H
=T
S

H SP =TdSVdP
d H SP
dP
=V
+T
dS
dS

Place the following restrictions: dP=0,dS0 we get :

H SP
=T
S

Prove:
d

H SP
=V
P

H SP =TdSVdP
d H SP
dS
=T
V
dP
dP

Place the following restrictions: dS=0,dP0 we get :

H SP
=V
S

Show:
d

A TV
=S
T

A TV =PdV SdT
d ATV
dV
=P
S
dT
dT

Place the following restrictions: dV=0,dT0 we get :

A TV
=S
T
TV

Show:

A
=P
V

TV

A =PdV SdT

d ATV
dT
=S
P
dV
dV
Place the following restrictions: dT=0,dV0 we get :

A TV
=P
V

Show:
d

GTP
=V
P

GTP =VdPSdT
d GTP
dT
=S
+V
dP
dP

Place the following restrictions: dT=0,dP0 we get :

GTP
=V
P
TP

Show:
d

G
=S
T

GTP =VdPSdT
TP

dG
dP
=V
S
dT
dT
Place the following restrictions: dP=0,dT0 we get :
TP

G
=S
P

(c )

The following relation is proved using Maxwells equations:

SP

T =V

S P

From useful relations obtained from Legendre Transformations we let T=

We the take the derivative

H SP
S

on both sides we obtain:

T SP H SP
=
(
)
P P S
Since the right hand side of the above equation has the same independent variables (S and V) for
both differentiations. We can rewrite the equation as follows:

SP

SP

T
H
=
P P S
T SP 2 H SP
=
P S P
T SP H SP
= (
)
P S P
Using relation obtained from Legendre Transforms (

V=

H SP

SP

We get:

= (V )
P S
SP

SP

T
V
=
P
S

The following relation is proved using Maxwells equations:

S TP =V T P
From useful relations obtained from Legendre Transformations we let S= -

We the take the derivative

TP

G TP
T

on both sides we obtain:

TP

S
G
=
(
)
P P T
Since the right hand side of the above equation has the same independent variables (S and V) for
both differentiations. We can rewrite the equation as follows:

STP 2 G TP
=
P
P T
STP 2 G TP
=
P
T P
STP GTP
=
(
)
P T P
TP

Using relation obtained from Legendre Transforms (

V=

TP

=
(V )
P T

We get:

STP V TP
=
P
T
U=S 2 V 2V 2 S

(d)

Find

U TV

and

Cv

Consider the given equation which describes U in terms of S and V (U=

SV

SV

SV

Therefore, by differentiating

T SV =

U SV

SV

U
U
P SV =
S
V

T=2SV and P=

We then obtain the following equation through substitution:

S TV =

we can find the equation for

T
2V

SV

with respect to S and V we obtain the following:

SV

). The function

U
U
dS +
dV
S
V
If we let:

SV

leads to a differential given by:

dU =

T=

. Therefore, to determine

TV

such that S=

U TV

S + 4 VS
dU =TdSPdV
S

TV

. Assuming that

. In the above case,

we must substitute the function

S TV into U SV

U TV =U SV (S TV , V )
U TV =(

T
T
) 2 V 2 (
)
2V
2V
TV

U =

Which simplifies to:

To calculate

Cv

Cv

we must differentiate

TV

T2
T
4V2

according to T. This is because the definition of

TV

is

U
T

The following show this mathematically:

Cv

U TV
T

U TV =

T2
TV
4V2

U TV T
= 2 V
T
V
T
V
V2

Cv=

T SV
V

(e) Show that:

Let T=

T SV
)
T PV
S

SP
V
V
(
)
S
(

T SV

, from the chain rule we obtain:

dT=

T
T
dS+
dV
S
V

SV

SV

dT T SV dS T SV
=
+
dV
S dV V

(Divide

through by dV)
By placing conditions on the following differential equation (P=0, V0) we get the
following:

T
V

T SV S
S V

T SV
V

T SV SVP T PV T SV
=

S V
V
V
SV

By placing the left hand side of the equation in fraction form (invert

T
S

get:
PV

S
)
V
STV
(
)
T
(

PV

SV

T
T

V
V

By rearranging the equation above we get:

SV

SV

T
V

Question 2

T
)
T
S

V
V SP
(
)
S
PV

term) we

TP

Ai) By definition: =

1 V
V T

, from the ideal gas equation we get

V TP =

RT
PV

We now substitute both equations into one another to get:

RT
(
)
PV
RT
(
)
T
PV
PV
R
RT
PV

Aii)

By definition:

1
T

1
TP
V
V
KT=
P
V TP =

, from the ideal gas equation we get

RT
PV

We now substitute both equations into one another to get:

RT
(
)
PV
RT
KT=
(
)
P
PV
KT=

PV RT
( 2 )
RT
P
KT=

Aiii)

1
P

1
H TP
C
= P
P
d

(1)

H SP=TdS +VdP

Divide through by dP:

d H SP
dS
=T
+V
dP
dP
Placing the restrictions the following restrictions: (dP0 ,dT=0) we get :

SP

TP

H
S
=T
P
P

+V

STP V TP
=

P
T

From Maxwell Relations (

PT

TP

H
V
=T
+V
P
T

(2)

Substituting (1) into (2):

1
V TP
=
(T
+V )
CP
T
=

1
V TP
(T
V )
Cp
T

(3)

1 V TP
V T

By definition =

Substituting into equation 3:

1
(TV V )
Cp

V
(T1)
Cp

However, is was shown that for an ideal gas =

Therefore:

1
T

V
1
(T ( )1)
Cp
T

V
(11)
Cp
=0

aiv)

U TV
Cp
T

C v =T
C v=

S TV
V
U SV S TV
S V

dS=

dS=

H TP
Cv
T
(T=

U SV

S
U TV
V

STV
S TV
dT +
dV
V
V
TV
Cv
P
dT +
dV
T
T

(1)

TP

TP

dS=

S
S
dT +
dP
T
P

dS=

Cp
dT
T

TP

S
dP
P

(2)

Equate equation (1) and (2):

TV
Cv
C
P
dT +
dV = p dT
T
T
T

TP

S
dP
P

Rearrange the equation into the following form:

( C pCv ) dT
T
d

T PV =

TV

TP

P
V
dV +
dP
T
T

T PV
T PV
dP+
dV
P
V
C
C

PTV
dV
T
V TP
T
( pC v )
dP+

T
T
dT =
( pC v )

Equating the coefficients of dP:

V TP T PV
( pC v )
=
T
P
T

C pC v
T
C pC v
T

V TP
T
PV
T
P
V TP PTV
T T

From the ideal gas equation the following expressions can be made:

V TP =

RT PV PV TV RT
,T =
,P =
P
R
V

TP

V
R
=
T
P

TV

P
T

R
V

Substituting the above relations in equation (3):

R
R
P
PV
V
( C pC v )=
R

(3)

( C pC v )

=R

( P+ Va )( V b) =RT

b) Van Der Waals equation:

The following equations are obtained through rearranging the above equation:

PV Pb a
ab
+
R
R VR R V 2

T PV =

TV

P =

RT
a

V b V 2

PTV
RT
a
=
+ 3
2
V
(V b) V
T PV P
a
2 ab
= 2
V
R V R RV3

Bi)

1 V TP
V T

a =

VP

T
PV 2 a 2 ab
a =V
=

+
V
R VR R V 2
1

1 T V P 1
(
)
V V

TV
2 a 2ab

+
( V b) VR R V 2

(substitute into eq. b)

TV
(V b)

2 a
(V b)
RV2

1
TV
2a
(

( V b ))
V b R V 2

a=

1
V TP
V
KT=
P

bii)

KT

PTV
RT V
a
=V
=
+ 2
2
V
(V b) V

K T 1=

R
TV
2a
(

( V b ))
V b V b R V 2
KT=

V b
a
R
=

biii)

V
(
Cp

V
(T1)
Cp

( ))

V
2 a V b

V b R T V 2

1)

biv)

Cp=Cv+

TV 2
KT

( V b ) a

Cp=Cv+

R
2
2 a (V b)
1
RT V 3

Cp-Cv=

R
2
2 a (V b)
1
RT V 3

=Cv+

TV 2