State Equation

 State of a gas can be described by its variables: n, P,T, and V.

 For a fix amount of gas (n is fixed), now the variables : P, T

and V. P&V relate to mechanical and T by heat.

 Mathematically : f(P,V,T) = constant

 U is a state function, then U = U(P,V,T)

 3x1023 coordinates to solve the problem. Therefore, we choose

any 2
 
 eg U = U(P,V) fix T U = U(V,T) fix P etc.
F  F ( x , y ), selanjutnya dF ditulis

(1.33)
Ada fungsi keadaan ini [F = F (x,y)] dengan syarat:

 Suppose U = U(P,V) constant T

 
 The Partial differential equation :
 U   U 
dU    dP    dV
 P  V  V  P
 What does it means?

 Take F = F(x,y)
 Then:  F   F 
dF    dx    dy
 x  y  y  x
 F = F(x,y) exists if:
 2F   2F 
    
 xy   yx 
 F is a state function F = F(x,y) and dF is called exact differential
 
   if 
 2
F    2
F 
 xy   yx  , F ≠ F(x,y), dF is inexact differential
  
   

 Consider dz = M(x,y)dx + N(x,y)dy in the form of

 F   F 
dF    dx    dy
 x  y  y  x
 F   F 
 by comparing M    and N    therefore
 x  y  y  x
 
 M    2F    2F 
   in 
the  of
N form
     
   y x  x  y  xy   yx 
 Process at constant Volume ( isochoric)

 Choose U = U(V,T) and dU = dq + dw

 at constant V we get dq V   U  dT then

   T  V
   dq   U 
    
 dT V  T V

 Define :  dq    U   C V
 dT  V  T  V

 where CV called heat capacity at constant V

 
 CV = a + bT + cT2 + …… ( temperature dependence)
 
 CV,m = CV /n called molar heat capacity
4
PROCESS AT CONSTANT PRESSURE
(ISOBARIC)
 Choose U = U(P,T) and first law followed by V = V(P,T)

 we then define:
,heat
dq 
CP    capacity at constant P
   dT  P

 CP = a + bT2 + cT3 + …. temperature dependence

   C P = CP,m =molar heat capacity at P constant

n

5
RELATIONSHIP CP and CV

 For ideal gas:

CP – CV = nR

Monoatomic molecule Cv = 1.5 R

Diatomic molecule Cv = 2.5 R

 For any gas :

  U    V 
C P  Cv   P     
  V T   T  P

6
ENTHALPY (H)

 Define H = U + PV
 
 dH = d(U + PV) and first law
 
 dH = dq + VdP

 at constant P dH = dq
 
 dH   dq 
 therefore       CP
 dT  P  dT  P

 dHP = dqP or

 ΔH = q
 

7
Internal Energy and ideal gas

  Ideal gas fullfil the following conditions

 i) state equation PV = nRT and

 U 
 ii)   0
 V T
 JOULE EXPERIMENT

 Joule measured temperature changes

when ideal gas expand adiabatically into a
vacuum.
thermometer

 The result observed that,

 no temperature change valve
Ideal Vacuum
Gas
(2)
 adiabatic : q = constant (1)

dq = 0 therefore q = 0
  insulator
 No work is done, Pext = 0 and dw = 0, w =0 Figure :Joule Experiment

 
 First law dU = dq + dw = 0 + 0 = 0
 Conclusion : w = 0
q =0
ΔU = 0
9
 Consider U = U (V, T):

 U   U 
dU    dV    dT
 V T  T V
 experiment data : dT = 0, dU = 0 therefore
 U 
0  dV
 V  T
 and dV ≠ 0 , therefore
 U 
  0
 V T
 U 
   is called internal pressure
 V  T

10
  U 
   = 0 for ideal gas
 V T
= small for other gas
= large for solid and liquid
U
 Question :    0 ?
 P T

 Results obtained from Joule’s experiment was not

satisfied due to heat capacity of water is very much
larger than gas, hence small change in temperature
difficult to detect.
JOULE-THOMSON EXPERIMENT
 Adiabatic process, q = 0, therefore U = w (First Law of
Thermodynamic)
  T1
Thermometer
T2
 Compartment A: wA = PA VA insulator
 Compartmen B: wB = -PBVB
wtotal = wA + wB
= PAVA + (- PBVB) A
PA
B
PB
 However,
U = UB - UA = wtotal Porous plate
compressed expanded
insulator
UB - UA = PAVA + (- PBVB)
UB + PBVB = UA + PAVA H = U + PV

HB = H A
HB – HA = H = 0
 Process occurs at constant enthalpy. 12
 ΔT detected, means cooling process
occurs during gas expansion. T (K)
 Joule-Thompson coefficient,  can be 700-
measured
600-
 
 T  T
   500-
 P  H P
400-
 During gas expansion, if the sign of  :
cooling heating
 positive – cooling 300-
 negative – heating 200-
 zero – no cooling & heating 100- Critical point
0-| | | | | |
 Temperature during expansion which  = 0
0 10 20 30 40 50
is called the inversion temperature.
P (mPa)
 Application: A gas can be used as a
refrigerant only at temperature below the Isenthalps and inversion temperature for N2
maximum inversion temperature, which is
607 K for N2, 204 K for H2 and 43 K for He.
13
 Using cylic rule:

 H 
 
 T   P  T
  
 P  H  H 
 
 T  P
 H 
 
 P  T

CP
Reversible Adiabatic Process for Ideal Gas

 nRT 
P 
 V 

CV dT nR
  .dV
T V

T2 V2
1 1
Cv 
T1
T
dT   nRV
V
dV
1

T2 V
C v ln   nR ln 2
T1 V1

15
Reversible Adiabatic
nR
Process for Ideal Gas
 1  CP  Cv  nR
CV

(a)  1
T2  V1 
CV CV
V1T1 nR
 V2T2 nR
or    CP
T1  V2  
CV


P1V1  P2V2 P2  V1 
(b) or   
P1  V2 

 1
(c) T1P11 T2P21 T2  P2 
or   
T1  P1 
16
 THERMOCHEMISTRY

 Heat effect during chemical and physical change

1. Constant Volume
qV = ΔU ( from first law)

2. Constant Pressure
qP = ΔH ( from dH = dq + VdP)

3. Chemical Reaction

Reactant Product
ΔH
 
ΔH = ΔU + Δ(PV) where
  Δ(PV) = (PV)product – (PV)reactant
17
 Case:

1. All products and reactants in solid or liquid phase, Δ(PV)

very small, hence ΔH ≈ ΔU so qP ≈ qV

2. If gas(gaseous) involved, Δ(PV) depends on the Δng :

Δng = ng(product) – ng(reactant) .

 For ideal gas

Δ(PV) = Δng RT
so
ΔH = ΔU + Δng RT
18
 EXAMPLE
The combustion of ethanol in a constant-volume calorimeter produces 1364.34 kJ
mol-1 at 298 K. what is the value of ∆H for the following combustion reaction?

C2H5OH(l) + 3O2(g)  2CO2(g) + 3H2O (l)

 
  ANSWER

∆H = ∆U + RT(∆n)
 
(∆n) = 2 - 3 = -1
 
Thus,
 
∆H = -1364.34 kJ mol-1x (8.314 JK-1mol-1 x 298 K x -1)

= - 1366.82 kJ mol-1

19
HESS’S LAW

 All state functions obey Hess Law (X = U, H, S, G and

A ; all are exact differential).
 The values depend on the final and initial states

20
 Heat of Reactions and Temperature

aA + bB mM + nN

 at particular T:

ΔHT = ( ∑HT(product ) - ∑HT(reactant) )

a) for two temperatures, T1 and T2 at constant P:

   H T 
    C P (product)    C P (Re ac tan t ) 
 T  P
 
 integrate limit between T1 and T2 :
  ΔH2 – ΔH1 = ∫ ΔCP dT where
 
ΔH2 at T2 and ΔH1 at T1
  if T1 and T2 not much different, CP assume to be constant, then
  ΔH2 – ΔH1 = ΔCP (T2 – T1)
b) With phase change
 ΔH from A to D ?
 Apply Hess law
 A to B + B to C + C + C to D + D

B C Liquid
P2 D
Solid

P1 A
Gas

T1 Tm T2 T
Phase changes for a component