KNC1023: Engineering Physical Chemistry

Chapter 3: The First Law of Thermodynamics

Relations between system properties

ASSOC. PROF. DR RUBIYAH BAINI

DEPARTMENT OF CHEMICAL ENGINEERING & ENERGY SUSTAINABILITY
Email: [email protected]
Tel: 082-583457
State and Path Functions
• So far, we’ve considered several state functions, Path 2 -
e.g., U and H Non-
adiabatic
• Value of a state function is independent of path Path 1 - w≠0;q≠0
• Depends on on initial and final state, e.g. U = Ufinal- Adiabatic
Uinitial w≠0;q=0
• Overall Change
U  initial
final
dU
dU is an exact differential

 Path from initial to final state has a functional

dependence
» Work and heat are path functions Upath1 = Upath2 = Uf -Ui
» When a system is heated, the total energy
transferred is the sum of all individual contributions
at each point of the path, it is not written as Δq.
 This path-dependence is an inexact differential. final
q initial , path
dq
Changes in Internal Energy, U(V,T)

 If U changes only as function of V (T constant)

U’ = U + (U/V)TdV [1]

 If U changes only as function of T (V constant)

U’ = U + (U/T)VdT [2]

 If U changes only as function of V and T

U’ = U + (U/V)TdV + (U/T)VdT [3]

 If change is infinitesimal, U’-U =dU and [3] becomes

dU = (U/V)TdV + (U/T)VdT [4]
 (U/T)V is Cv
 (U/V)T is called the internal pressure, πT

[4] becomes dU = πTdV + CvdT

Internal Pressure, πT
• For ideal/perfect gas, πT = 0,
meaning the internal energy is
independent of the volume
occupied by the sample

• For real gas,

If dU >0 as dV increases with T
constant, attractions between
molecules dominate and πT > 0
If dU <0 as dV increases with T
constant, repulsions between
molecules dominate and πT <0
 Changes in U and H with T
The relationship of U and H
with temperature gives the
heat capacity at constant
volume, Cv, and the heat
capacity at constant volume,
Cp

 U 
   Cv
 T  p

 H 
   Cp The plot shows the changes in the
 T  p internal energy, U and enthalpy with
temperature, T.
Change in Internal Energy - Constant
P
The internal energy, U, changes with temperature at constant pressure
dU   T dV  C V dT
U    T dV  C V dT
    
T p  T p
U  V 
    T    C V
T p T p

The change in volume with temperature at constant pressure is related to the

thermal compressibility of the gas, 
   
1 V V
   or    V
V T p T p
U 
so     T V  C V
T p
• Large  means sample responds strongly to changes in T
• For an ideal gas, T = 0 so

 U   U 
   CV  
 T  p  T  p
Enthalpy, H (p,T)

• Like U, H is a state function  By analogy to  earlier, the isothermal

• For closed system with constant composition compressibility, T,
1 V  V 
T     or     T V
 H   H  V  p T  p T
dH    dp    dT
 p T  T  p so
 H  p  1
and    Cp
 T  p   
T V T 
 H     T V
sodH    dp  C p dT V p
 p T
• At constant volume  
 
y  1 
by reciprocal identity,    x  ,
H  H   p  x z   
        C p 
 y z 

T V p T T V
• By the chain rule, we can find (p/T)V T  1 V 
   V  and we know    V
V p T p
 
T p
y  x  z 
Chain Rule : if z  z(x,y) then        1 T  1
x z z y y x so   
V p V
Re call p(V,T) p  
This makes   
p  1 T V  T
  
T V T  V  H  H  
    and       Cp
V p  p T T V  p T  T
Enthalpy, H (p,T)
• To evaluate HpT apply chain rule and reciprocal identity again
H  1
   Euler chain rule
 p T  T   p 
   
H p T H
H  H  T 
        reciprocal relation 2x
 p T T p p H

• But, Cp= (H/T)p and if one defines (T/P)H as µ, then HpT =- Cpµ
• Thus, H  H  
      Cp
T V  p T  T
H  
   C p   Cp
T V T μ – Joule-Thomson coefficient
or
H    
   C p 
1    
T V  T 
Isothermal compressibility, 

 If the pressure increases, the volume decreases so if dp is positive,

dV is negative
◦ Since (1/V)(V/p)T,  is always positive
 For and ideal gas V=nRT/p so
(V/p)T= -nRT/p2 and (1/V)(-nRT/p2 )
Simplifying 
(nRT /V)(1/p2 )
(p)(1/p2 )
(1/p )
 This means that as the pressure increases, the compressibility of a gas decreases
Relationship between Cv and Cp
IdealGas
• For ideal gases, Cp = Cv +nR
• Proof:

H 
C p   
T p
Re call H  U  pV
U 
for ideal gas pV  nRT and Cv   
T p
H  U   nRT   U 
so C p              nR
T p T p  T p T p
U 
C p     nR  Cv  nR or C p  Cv  nR
T p
Relationship between Cv and Cp
Real Gases
• For real gases, we can use some basic definitions and what we’ve already learned
to find Cp -Cv :
V 
H  U  C p  Cv  p    T V
C p    and Cv    definition T p
T p T V
and H  U  pV definition 1 V 
but the expansion coefficient,     ,
H  U  V T p
C p  Cv      
T p T V V 
or    V
U  pV   U  T p
C p  Cv         


  T p   T  T V
p  C p  Cv  pV   T V  Vp   T 
pV  U  U  p 
or C p  Cv          Now  T  T    p [see Chapter 5]
 T p T p T V
T V
U 
but earlier we saw     T V  Cv  p    p 
 T p so C p  Cv  VT      VT 
 T   TV
U 
 V 
and    Cv p 
T V 
   [proved earlier]
pV  T V  T
so C p  Cv      T V  Cv  Cv
 T p     2 VT
so C p  Cv  VT 
 

V   T   T
C p  Cv  p    T V
T p
 For ideal gas =1/T and T=1/p and this reduces to what we found earlier