Chapter 4 : Second Law of Thermodynamics

Example 4.1, Page no:90

In [21]:
# Variables
#Given:
T1 = 700.; 			#temperature of heat source(K)
T2 = 300.; 			#temperature of heat sink(K)

# Calculations
#To calculate the maximum efficiency
eff=((T1-T2)/T1); 			#efficiency of a heat engine

# Results
print 'Maximum efficiency of heat engine is %f'%eff
Maximum efficiency of heat engine is 0.571429

Example 4.2, Page no:90

In [22]:
# Variables
#Given:
m = 1.; 			#mass of water(kg)
T1 = 300.; 			#temperature of surrounding(K)
T2 = 273.; 			#temperature of water(K)
Hf = 334.11; 			#latent heat of fusion of ice(kJ/kg)

# Calculations and Results
#To determine minimum amount of work and heat given upto surrounding
#(a)
Q2 = m*Hf; 			#heat absobed at temperature T2
W = ((Q2*(T1-T2))/T2); 			#minimumm amount of work required
print 'Minimum amount of work required is %f kJ'%W
 
#(b)
#Q1 is the heat given up the surrounding
Q1 = W+Q2;
print 'Heat given upto surrounding is %f kJ'%Q1
Minimum amount of work required is 33.043846 kJ
Heat given upto surrounding is 367.153846 kJ

Example 4.3, Page no:90

In [23]:
# Variables
#Given:
P_out = 4.5; 			#output power(hp)
P_in = 6.25; 			#input power(kW)
T1 = 1000.; 			#source temperature(K)
T2 = 500.; 			#sink temperature(K)

# Calculations and Results
#To determine efficiency of proposed engine 
ep = ((P_out*745.7)/(P_in*1000)); 			#proposed efficiency
print 'Efficiency of proposed engine is %f'%ep

em = ((T1-T2)/T1); 			#maximum efficiency
print 'The maximum efficieny is %f'%em
print 'Hence the claim of the proposed engine is impossible'
Efficiency of proposed engine is 0.536904
The maximum efficieny is 0.500000
Hence the claim of the proposed engine is impossible

Example 4.4, Page no:93

In [24]:
# Variables
#Given:
P = 500.; 			#pressure of dry saturated steam(kPa)

#From steam tables
Hv = 2106.; 			#latent heat of vaporisation(kJ/kg)
T = 425.; 			#saturation temperature(K)
 
# Calculations 
#To calculate the entropy of evaporation
#By equation 4.25 (Page no. 93)
Sv = (Hv/T); 			#entropy change accompanying vaporisation

# Results
print 'Entropy of evaporation is %f kJ/kg K'%Sv
Entropy of evaporation is 4.955294 kJ/kg K

Example 4.5, Page no:94

In [25]:
# Variables
#Given:
m = 2.; 			#mass of gas(kg)
T1 = 277.; 			#initial temperature(K)
T2 = 368.; 			#final temperature(K)
Cv = 1.42; 			#specific geat at constant volume(kJ/kg K)

# Calculations
import math
#Using equation 4.31 (Page no. 94)
S = (m*Cv*math.log(T2/T1)); 			#change in entropy(kJ/K)

# Results
print 'Change in entropy is %f kJ/K'%S
Change in entropy is 0.806746 kJ/K

Example 4.6, Page no:94

In [26]:
#Given:
T = 300.; 			#temperature in K
P1 = 10.; 			#initial pressure(bar)
P2 = 1.; 			#final pressure(bar)
R = 8.314; 			#ieal gas constant

# Calculations
import math
#To calculate the entropy change
#Using equation 4.33(Page no. 94)
S = (R*math.log(P1/P2)); 			#(kJ/kmol K)

# Results
print 'Entopy change is %f kJ/kmol K'%S
Entopy change is 19.143692 kJ/kmol K

Example 4.7, Page no:94

In [27]:
# Variables
#Given:
T1 = 335.; 			#initial temperature in K
T2 = 300.; 			#final temperature in K
P1 = 10.; 			#initial pressure(bar)
P2 = 1.; 			#final pressure(bar)
Cp = 29.3; 			#specific heat constant at constant pressure(kJ/kmol K)
R = 8.314; 			#ideal gas constant

# Calculations
import math
#To determine change in entropy
#Using equation 4.30 (Page no. 94)
S = ((Cp*math.log(T2/T1))-(R*math.log(P2/P1))); 			#entropy change(kJ/kmol K)

# Results
print 'Entropy change in the process is %f kJ/kmol K'%S
Entropy change in the process is 15.910494 kJ/kmol K

Example 4.8, Page no:95

In [28]:
# Variables
#Given:
m1 = 10.; 			#mass of water at 375 K (kg)
m2 = 30.; 			#mass of water at 275 K (kg)
c = 4.2; 			#specific heat of water (kJ.kg K)

# Calculations
import math
#To determine the change in entropy
#Let T be the final temperature(K)
T = ((m1*375)+(m2*275))/(m1+m2);
#S1 be change in entropy for hot water
S1 = (m1*c*math.log(T/375)); 			#[kJ/K]
#S2 be the change in entropy for cold water
S2 = (m2*c*math.log(T/275)); 			#[kJ/K]
#S be the total entropy change
S = S1+S2; 

# Results
print 'The total entropy change is %f kJ/K'%S
The total entropy change is 1.591404 kJ/K

Example 4.9, Page no:95

In [29]:
# Variables
#Given:
m1 = 35.; 			#mass of steel in kg
m2 = 150.; 			#mass of oil in kg
T1 = 725.; 			#temperature of steel(K)
T2 = 275.; 			#temperature of oil(K)
c1 = 0.88; 			#specific heat of steel (kJ/kg K)
c2 = 2.5; 			#specific heat of oil(kJ/kg K)

# Calculations
import math
#To calculate the total entropy change
#Let T be the final temperature
T = (((m1*c1*T1)+(m2*c2*T2))/((m1*c1)+(m2*c2)));
#S1 be the in entropy for steel
S1 = (m1*c1*math.log(T/T1)); 			#[kJ/K]
#S2 be the change in entropy for oil
S2 = (m2*c2*math.log(T/T2)); 			#[kJ/K]
#S be the total entropy change
S = S1+S2;

# Results
print 'The total entropy change is %f kJ/K'%S
The total entropy change is 17.649827 kJ/K

Example 4.10

In [30]:
# Variables
#Given:
n1 = 0.21; 			#volume % of oxygen in air
n2 = 0.79; 			#volume % of nitrogen in air
R = 8.314; 			#ideal gas constant

# Calculations
import math
#To calculate entropy of 1 kmol of air
#Using equation 4.35 (Page no. 96)
S = (-R*(n1*math.log(n1)+n2*math.log(n2))); 			#[kJ/kmol K]

# Results
print 'The total entropy change is %f kJ/kmol K'%S
The total entropy change is 4.273036 kJ/kmol K

Example 4.11

In [31]:
# Variables
H = -2.8318*10**5; 			#heat of reaction (J/mol)
T = 298.; 			#temperature of reaction in K
#Absolute entropies for CO, O2, CO2 are (in J/mol K)
S_CO = 198.;
S_O2 = 205.2;
S_CO2 = 213.8;

# Calculations and Results
# To determine the change in entropy for the reaction
# Referring equation 4.36 (Page no. 96)
S_reactant = S_CO + 0.5*S_O2; 			#entropy change for reactants
S_product = S_CO2; 			#entropy change for products
S = S_product-S_reactant; 			#total entropy change
print 'The total entropy change for the reaction is %f J/mol'%S
print 'Since the reaction is highly irreversible, entropy change cannot be calculated as the ratio of heat of reaction to the temperature'

#The energy available for useful work is the difference between heat of reaction and entropy energy due to ireversible nature of the process
W_useful = -H+(T*S); 			#energy available for useful work (J)
print 'Energy available for useful work is %3.2e J'%W_useful
The total entropy change for the reaction is -86.800000 J/mol
Since the reaction is highly irreversible, entropy change cannot be calculated as the ratio of heat of reaction to the temperature
Energy available for useful work is 2.57e+05 J

Example 4.13

In [32]:
# Variables
#Given:
H_steam = 2923.5; 			#enthalpy of superheated steam (kJ/kg)
S_steam = 6.71; 			#entropy of superheated steam (kJ/kg K)
H_liquid = 845.; 			#enthalpy of saturated liquid (kJ/kg)
S_liquid = 2.32; 			#entropy of saturated liquid (kJ/kg K)
T = 300.; 			#temperature of system (K)

# Calculations
#To calculate change in entropy and check whether the process is reversible
S_system = S_liquid-S_steam; 			#change in entropy of steam

#Let Q be the heat given out during condensation
Q = -(H_liquid-H_steam);
S_surrounding = Q/T; 			#change in entropy of the surrounding
S_total = S_system+S_surrounding; 			#total entropy change

# Results
print 'The total entropy change is %f kJ/kg'%S_total
print 'Since total entropy change is positive,the process is irreversible'
The total entropy change is 2.538333 kJ/kg
Since total entropy change is positive,the process is irreversible

Example 4.14

In [33]:
# Variables
#Given:
V = 1.; 			#volume of each compartment in cubic meters
P_sat = 683.6; 		#pressure of saturated steam (kPa)
P_steam = 101.3; 	#pressure of supereated steam (kPa)
T_sat = 437.2; 		#temperature of system (K)

#Referring steam tables
#For saturated steam at pressure 683.6 kPa and temp 437.2 K
H_sat = 2761.; 			    #enthalpy of saturated steam (kJ/kg)
S_sat = 6.7133; 			#entropy of saturated steam (kJ/kg K)
spvol_sat = 278.9*10**-3; 	#specific volume of saturated steam (cubic m/kg)
U_sat = 2570.4; 			#specific internal energy of saturated steam (kJ/kg)

#For superheated steam at 101.3 kPa and 437.2 K
H_steam = 2804.; 			    #enthalpy of superheated steam (kJ/kg)
S_steam = 7.6712; 			    #entropy of superheated steam (kJ/kg K)
spvol_steam = 1976.2*10**-3; 	#specific volume of superheated steam (cubic m /kg)
U_steam = 2603.3; 			    #specific internal energy of superheated steam (kJ/kg)


# Calculations
#To determine the change in entropy of system
m_sat = V/spvol_sat; 			#mass of satureated steam(kg)
m_steam = V/spvol_steam; 		#mass of superheated steam (kg)
m_sys = m_sat+m_steam; 			#mass of system (kg)
spvol_sys = (2.*V)/m_sys; 		#specific volume of system (cubic m/kg)
			#Since no heat exchange and work interaction occurs so internal energy after mixing remains the same
U1_sat = m_sat*U_sat; 			    #internal energy of saturated steam (kJ)
U1_steam = m_steam*U_steam; 	    #internal enegy of superheated steam (kJ)
U_sys = (U1_sat+U1_steam)/m_sys; 	#specific internal energy of system (kJ/kg)

#Referring steam tables
#At calculated U_sys and spvol_sys
S_sys = 6.9992; 			               #specific entropy of system (kJ/kg K)
Si = ((m_sat*S_sat)+(m_steam*S_steam));    #initial entropy of system (kJ/K)
Sf = (m_sys*S_sys); 			           #final entropy of system (kJ/K)
S = Sf-Si; 			                       #change in entropy

# Results
print 'The change in entropy of the system is %f kJ/K'%S
print 'Since entropy change is positive, the process is irrevresible'
The change in entropy of the system is 0.685052 kJ/K
Since entropy change is positive, the process is irrevresible

Example 4.15

In [34]:
# Variables
#Given:
V = 1.; 			#volume of each compartment in cubic m
T = 300.; 			#temperature of ideal gas in 1st compartment (K)
P = 200.; 			#pressure of ideal gas in 1st compartment (kPa)
R = 8.314; 			#ideal gas constant

# Calculations
#To calculate entropy change
#Let n be the number of moles of gas
n = ((P*V)/(R*T));
#Since gas in vessel exchanges no heat and work with surrounding so internal energy remains same
#This implies temperature after mixing is same as that before mixing

#Final conditions:
Tf = 300.; 			#final temperature (K)
Vf = 2.; 			#final volume (cubic m)
Pf = 100.; 			#final pressure (kPa)

#Initial conditions:
Ti = 300.; 			#initial temperature (K)
Vi = 1.; 			#initial volume (cubic m)
Pi = 200.; 			#initial pressure (kPa)
import math
#Using equation 4.33 (Page num 94)
S = n*R*math.log(Vf/Vi); 			#entropy change of system (kJ/K)
#Since entropy of surrounding does not change
S_total = S; 			#total entropy change

# Results
print 'The change in total entropy is %f kJ/K'%S_total
The change in total entropy is 0.462098 kJ/K

Example 4.16

In [35]:
# Variables
#Given:
m_oil = 5000.; 			#mass flow rate of oil (kg/h)
Tin_oil = 500.; 			#inlet temperature of oil (K)
Tin_water = 295.; 			#inlet temperature of water (K)
c_oil = 3.2; 			#specific heat of oil (kJ/kg K)
c_water = 4.2; 			#specific heat of water (kJ/kg K)
import math
#To calculate entropy change in the process
#Assuming oil is cooled to minimum permissible temperature
Tout_oil = 305.; 			#exit temperature of oil (K)
Tout_water = 490.; 			#exit temperature of water (K)

# Calculations
#Let m_water be the mass flow rate of water
#By enthalpy balance
m_water = ((m_oil*c_oil*(Tin_oil-Tout_oil))/(c_water*(Tout_water-Tin_water)));  			#(kg/h)
S_oil = m_oil*c_oil*math.log(Tout_oil/Tin_oil); 			#entropy change of oil (kJ/K)
S_water = m_water*c_water*math.log(Tout_water/Tin_water); 			#entropy change of water (kJ/K)
S_tot = S_oil+S_water; 			#total entropy change

# Results
print 'The total entropy change in the process is %f kJ/K'%S_tot
The total entropy change in the process is 210.139407 kJ/K

Example 4.17

In [36]:
# Variables
#Given:
To = 275.; 			#temperature of quenching oil (K)

# Calculations
S_steel = -26.25; 			#change in entropy os casting (kJ/K)
S_oil = 43.90; 			#change in entropy of oil (kJ/K)
S_tot = S_steel+S_oil; 			#total entropy change
#Let W be loss in capacity for doing work
W = To*S_tot; 			#(kJ)

# Results
print 'The loss in capacity for doing work is %f kJ'%W
The loss in capacity for doing work is 4853.750000 kJ

Example 4.18

In [37]:
import math
#Given:
m_oil = 5000.; 			    #mass flow rate of hydrocarbon oil (kg/h)
Tin_oil = 425.; 			#inlet temperature of oil (K)
Tout_oil = 340.; 			#exit temperature of oil (K)
m_water = 10000.; 			#mass flow rate of water (kg/h)
Tin_water = 295.; 			#inlet temperature of water (K)
c_oil = 2.5; 			    #mean specific heat of oil (kJ/kg K)
c_water = 4.2; 			    #mean specific heat of water (kJ/kg K)

#To determine total change in entropy and available work

# Calculations and Results
#(a)
#By energy balance
Tout_water = ((m_oil*c_oil*(Tin_oil-Tout_oil))/(m_water*c_water))+295; 			#exit temperature of water (K)
S_oil = m_oil*c_oil*math.log(Tout_oil/Tin_oil); 			#change in entropy of oil (kJ/K)
S_water = m_water*c_water*math.log(Tout_water/Tin_water); 			#change in entropy of water (kJ/K)
S_tot = S_oil+S_water; 			#total entropy change
print 'The total entropy change is %f kJ/K'%S_tot


#(b)
To = 295.; 			#temperature at which heat is rejected to surrounding (K)
#Let Q be heat given out by the oil on cooling
Q = m_oil*c_oil*(Tin_oil-Tout_oil);
#Heat rejected to the surrounding at To by the Carnot Engine is given by
#Q2 = To(Q/T) = -To*S_oil
Q2 = -To*S_oil; 			#(kJ)
#Let W be the work output of engine
W = Q-Q2;
print 'The work output of the engine would be %4.3e kJ'%W
The total entropy change is 666.266812 kJ/K
The work output of the engine would be 2.397e+05 kJ

Example 4.19

In [38]:
# Variables
#Given:
T = 10.; 			#temperature of metal (K)
Cp = 0.45; 			#molar heat capacity at 10 K (J/mol K)

# Calculations
#To determine the molar entropy of metal
#Entropy of solid at 10 K is calculated using first integral in equation 4.55 (Page no. 108)
S = Cp/3;

# Results
print 'Molar entropy of meatl at 10 K is %f J/mol K'%S
Molar entropy of meatl at 10 K is 0.150000 J/mol K

Example 4.20

In [39]:
# Variables
#Given:
T = 473.; 			#temperature at entropy is to be determined (K)
Tf = 273.; 			#base temperature (K)
Tb = 373.; 			#boiling temperature (K)
Cpl = 4.2; 			#avearge heat capacity of water (kJ/kg K)
Cpg = 1.9; 			#avearge heat capacity of water vapour between 373 K and 473 K
Hv = 2257.; 			#latent heat of vaporisation at 373 K (kJ/kg)

# Calculations
import math
S = (Cpl*math.log(Tb/Tf))+(Hv/Tb)+(Cpg*math.log(T/Tb));


# Results
print 'Absolute entropy of water vapour at 473 K and 101.3 kPa is %f kJ/kg K'%S
print 'It compares favourably with the value reported in steam tables'
Absolute entropy of water vapour at 473 K and 101.3 kPa is 7.813068 kJ/kg K
It compares favourably with the value reported in steam tables