CHEMICAL ENGINEERING

THERMODYNAMICS
 Ideal Gas Equation

PV  nRT Values for Universal Gas

constant
PM
 ft  lb f
RT R  8.314
J
 1545
mol  K lbmol  R
V RT
v   0.08206
Li  atm
 10.73
ft 3  psia
m PM mol  K lbmol  R
cal BTU
 1.98  1.98
mol  K lbmol  R
 Universal Gas Constants

Value of Universal Gas Constant:

R = 8.314 J/mol-K = 1545 ft-lbf/lbmol-R

3
= 0.08206 Li-atm/mol-K = 10.73 ft -psi/lbmol-R
= 1.986 cal/mol-K = 1.986 BTU/lbmol-R

For steam:
R = 0.462 kJ/kg-K = 85.8 ft-lbf/lb-R

For air:
R = 0.286 kJ/kg-K = 53.3 ft-lbf/lb-R
 PROPERTIES OF WATER AND AIR

Values of Specific Heats:

For water: C p (liquid)  4.186 kJ/kg-K = 1 BTU/lb-R

C p (solid)  2.1 kJ/kg-K = 0.5 BTU/lb-R
C p (vapour )  1.9 kJ/kg-K = 0.45 BTU/lb-R
For air: C p (air )  1 kJ/kg-K = 0.24 BTU/lb-R

Values of Latent Heat for Water:

at 0C, h fusion  80 cal/g = 33.5 kJ/kg

at 100C, hvaporization  540 cal/g = 2255 kJ/kg
GENERALIZED EOS
 FIRST LAW OF THERMODYNAMICS

Work: W  V2 PdV
 V1

Heat: constant P: Q  nC p T2  T1 

Rudolf Clausius, 1850
constant V: Q  nCv (T2  T1 )

First Law of Thermodynamics U  Q  W

NON-FLOW PROCESSES
 NON-FLOW PROCESSES
PROCESS W (ideal ) ΔU Q
Isothermal
V  P 
mRT ln  2  =mRT ln  1 
 V1   P2 
0 W
Isochoric

0 mCv T2  T1  mCv T2  T1 

Isobaric

Pex V2  V1  mCv T2  T1  mC p T2  T1 

Adiabatic
mR T2  T1  mR T2  T1 
0
k 1 k 1
Polytropic
mR T2  T1 
mR T2  T1  (n  k)
mR T2  T1 
(n  1)(k  1)
n 1
k 1  nk 
mC n T2  T1   m  Cv  T2  T1 
 n 1 
 Polytropic and Adiabatic Processes
POLYTROPIC ADIABATIC

P vs. V: n
P1V1  P2V2 n P vs. V: P1V1k  P2V2k
T vs. V: T1V1 n1
 T2V2 n1 T vs. V: T1V1k 1  T2V2k 1
n 1 k 1
T2  P2  n T2  P2  k
T vs. P:   T vs. P:  
T1  P1  T1  P1 

kJ btu
Mayer relation: C p  Cv  R For air, C p  1  0.24
kg  K lb  R
kJ btu
Cv  0.714  0.1714
kg  K lb  R
Values of Cv, Cp and Υ
 Pure Substances
Properties of Pure Substances

Quality of steam: mg
x
mg  ml

h  xhg  (1  x)hl s  xsg  (1  x)sl

u  xug  (1  x)ul v  xvg  (1  x)vl
 STEAM TABLE SHORTHANDS

Steam Table Short-cuts: hf  4.186(T  273) kJ/kg

hg  1.636T  2064.2 kJ/kg all T in Kelvins,K

hfg  3207  2.55T kJ/kg

To convert to BTU/lb multiply by 0.43

h in BTU/lb = 0.43  (h in kJ/kg)
 FLOW PROCESSES

Continuity Equation (Mass Conservation): m  vA

where 𝐴𝑐 = cross-sectional area of pipe.

Engineering Bernoulli Equation:

v22  v12 g  z2  z1  P2  P1
    F  Q  Ws
2gc gc 

v22  v12 g  z2  z1 
  H2  H1  Q  Ws
2gc gc
Note: the kinetic and potential energy terms must be divided by g c
in all cases. That is gc = 1 for mks(SI) and gc = 32.174 for
fps(English)
Important Conversions!
2
m
1 2  1 kgJ
s
ft lb f
1 hp  746 W 1 hp  550 s
1 BTU  778 ft  lb f
 FLOW PROCESSES AND THERMODYNAMIC DEVICES

v22  v12
Nozzle and Diffusers  (h2  h1 )
2gc

 v22  v12 gz P2  P1 

Pumps (liquids) Ws  m    
 2g g 
 c c 
  Ws W
a
kmR(T2  T1 )
Compressor (gas/vapour) Ws 
k 1
  Ws W
a
v22  v12
Fans and Blowers Ws  m
2gc
  Ws W
a

Turbine
Ws   h2  h1  m
  Wa W
s
 ENTROPY AND SECOND LAW
Q
ENTROPY, S: S 
T

 T2   V2 
Entropy of Ideal Gas: S  nCV ln    nR ln  
 T1   V1 
 T2   P2 
S  nCP ln    nR ln  
 T1   P1 
T 
Entropy of Solids/Liquids: S  mC p ln  2 
 T1 
 CARNOT ENGINE

Ideal Carnot Engine:

QH  W  QC
Sadi Carnot

W QH  QC TH  TC
  
QH QH TH
S  0
For non-ideal engines:
Availability(Exergy)  Wmax  QH  TH S
actual Wactual
Second Law Efficiency  II  
Carnot QH  TH S
 CARNOT REFRIGERATOR AND HEAT PUMP

Ideal Carnot Refrigerator & Heat Pump: Q  W  Q

H C

QC QC TC
Refrig: COPR   
W QH  QC TH  TC
QH QH TH
Heat Pump: COPhp   
W QH  QC TH  TC
 GAS POWER CYCLES
1
Otto  1 
r k 1
Otto Cycle Compression ratio: r 
V1
with spark-ignition V2

1  rc n  1 
Diesel  1  n1 
rk  n(rc  1) 
 
V1
compression ratio = r 
Diesel Cycle V2
V3
No spark-ignition cut-off ratio = rc 
V2
expansion ratio: r = rc  re

1
 1
rp(k 1)/ k
Brayton Cycle pressure ratio: rp 
PH
Gas-turbine engines PL
T2  T1
Back-work ratio: BWR 
T3  T4
 Important Notes on ICE
Mean Effective Pressure (MEP)

MEP Vmax  Vmin   W

Vapour Power Cycle(Steam Power Plant)

h2 ' h1
WT  h3  h4  T (h3  h4 ') WP  h2  h1 
P
QH  h3  h2 QC  h4  h1

WT ' WP ' (h3  h4 ')  (h2 ' h1 )

Plant Eff. = o  
QH ' (h3  h2 ') 1
b
Vapour Compression Cycle Refrigeration

Qc h1  h4
COP  
h1  h1g W h2  h1
s2  s1g
A ‘‘ton’’ of refrigeration is supposedly the heat
h3  h4  h3f rate necessary to melt a ton of ice in 24 hours.
By definition,
h4  h4f  x4 h4fg
1 ton of refrigeration = 3.52 kW
1 ton of refrigeration = 12,000 Btu/hr
Refrigerants and Nomenclature:
 SOLUTIONS THERMODYNAMICS
NON-IDEAL SOLUTIONS Fugacity, f- measure of escaping
tendency of a gas
 i xPi sat
yi 
PT
 K i xi  Modified Raoult Eq. Bubble Calculation:  yi  1
GAS-PHASE EQUILIBRIA
DewPoint Calculation:  xi  1
 f 
Gi  Gi ig
 Gi  RT  yi ln 
R

y P
 i 
Gi R  RT  yi ln i 

LIQUID-PHASE EQUILIBRIA

a
Gi  Gi ig
 Gi  RT  xi ln  
E
 Ci 
Gi E  RT  xi ln   i 
 PROBLEM 1
Calculate molar (cm^3/mol) for ethylene at 298.15 K and
12 bar by the following equations:

The Redlich-Kwong equation.

A. 1916.5 B. 1918.0 C. 1900.0 D. 1920.3

The Soave-Redlich-Kwong equation.

A. 1916.5 B. 1918.0 C. 1900.0 D. 1920.3

The Peng-Robinson equation.

A. 1916.5 B. 1918.0 C. 1900.0 D. 1920.3
 PROBLEM 2
How much heat is required in order to vaporize
25 lbs of water from 104°F to steam at 257°F
with quality of 70%?

A. 14,500 BTU C. 23,400 BTU

B. 20,300 BTU D. 32, 500 BTU
 PROBLEM 3
A perfect gas (MW = 26.28) has a polytropic
constant of 1.26. If 20 Btu are added to 10 lbs of
this gas at constant volume when initial
temperature is 90°F, find the final temperature.

A. 97°F B. 104°F C. 154°F D. 185°F

 PROBLEM 4
Ten cubic feet of air are cooled at a constant
pressure of 80 psia. The initial temperature was
180°F and the final temperature after cooling is
100°F. Calculate the change of internal energy:

A. -46.3 BTU C. -41.2 BTU

B. -56.7 BTU D. -67.8 BTU
 PROBLEM 5
An insulated chamber with a breakable
compartment in between. One side is 3 m3 of
empty space and the other side contains 2 m3
of helium at 30C and 3 atm. Determine the
entropy change (J/K) when the compartment is
punctured:

A. 1220 C. 1670
B. 1840 D. 0
 PROBLEM 6
Air enters an insulated nozzle at negligible speed at
60 psia and 80degF at 20 lb/min. The exit pressure
is at 14.7 psia. Determine the exit velocity:

A. 960 fps
B. 340 fps
C. 1460 fps
D. 2300 fps
 PROBLEM 7
A steam turbine operates adiabatically at a power level of
3500 kW. Steam enters the turbine at 2400 kPa and
773.15 K (500°C) and exhausts from the turbine as
saturated vapor at 20 kPa.

What is the steam rate through the turbine in kg/sec:

A. 4.103 B. 7.23 C. 1.26 D. 5.89

what is the turbine isentropic efficiency?

A. 0.721 B. 0.819 C. 0.963 D. 0.873
 PROBLEM 8
A turbine receives 150 lbm/s of air at 63 psia
and 2450°R and expands it polytropically to 14.7
psia. The exponent n is equal to 1.45 for the
process. Determine the power.

A. 23,856 BTU/s C. 41,700 HP

B. 52,343.16 kW D. 53,343.16 ft-lb/s
 PROBLEM 9
A fan is powered by 0.5 hp motor and delivers
air at a rate of 85 m3/min. Determine the
highest value for the average velocity of air
mobilized by the fan.
A. 18.23 m/s B. 21.12 m/s
C. 25.34 m/s D. 32.23 m/s
 PROBLEM 10
A Carnot cycle has a sink temperature of 100°F
and a cycle efficiency of 70%. Find the
temperature of the heat source.

A. 1306.70°F B. 1406.70°F
C. 1506.70°F D. 1606.70°F
 PROBLEM 11
A Carnot cycle has a maximum temperature of
550°F and minimum temperature of 100°F. If the
heat added is 4200 Btu/min, find the
horsepower output of the engine.

A. 34.53 B. 40.56 C. 44.13 D. 65.40

 PROBLEM 12
A reverse Carnot cycle requires 3 Hp and
extracts energy from a lake to heat a house. If
the house is kept at 70°F and requires 2000 Btu
per minute, what is the temperature of the lake?

A. 35.29°F B. 36.29°F
C. 39.29°F D. 40.29°F
 PROBLEM 13
A heat engine receives heat from a source at
1200 K at a rate of 500 kJ/s and rejects the
wasted heat to a sink at 300 K. If the power
output of the engine is 200 kW, the second law
efficiency of this heat engine is?

A. 35% B. 40% C. 53% D. 75%

 PROBLEM 14
A rigid vessel of 0.06 m3 volume contains an
ideal diatomic gas, at 500 K and 1 bar. If heat in
the amount of 15 kJ is transferred to the gas,
determine its entropy change in J/K:

A. 20.794 B. 24.632
C. 14 .632 D. 10.794
 PROBLEM 15
A steel casting at a temperature 725 K and
weighing 35 kg is quenched in 150 kg oil at 275
K. If there are no heat losses, determine the
change in entropy. The specific heat of steel is
0.88 kJ/kg K and that of oil is 2.5 kJ/kg K.

A. 14.32 kJ/K C. 11.33 kJ/K

B. 17.65 kJ/K D. 10.31 kJ/K
 PROBLEM 16
An Otto cycle engine has an initial air pressure and
temperature of 14.7 psia and 60°F. 750 Btu of heat is
supplied per lbm of air at the end of compression. The
compression ratio is 7. Find

the thermal efficiency

A. 54.1% B. 45.7% C. 12.4% D. 67.8%

the mean effective pressure for the cycle. Assume ideal

conditions:
A. 230 psi B. 195 psi C. 340 psi D. 150 psi
 PROBLEM 17
A diesel engine intakes atmospheric air at
60degF and adds 800 Btu/lbm of energy. If the
maximum pressure is 1200 psi, calculate the
thermal efficiency:
A. 45.78% B. 63.51%
C. 26.78% D.83.4%
 PROBLEM 18
In an air-standard Brayton cycle the inlet
temperature and pressure are 20°C and 101.325
kPa. The turbine inlet conditions are 1200 kPa
and 900°C. Determine the air flow if the turbine
produces 12 MW.
A. 21.41 kg/s B. 20.20 kg/s
C. 19.25 kg/s D. 18.10 kg/s
 PROBLEM 19
Consider a steam power plant operating on the simple ideal Rankine
cycle. Steam enters the turbine at 3 MPa and 350oC and is condensed
in the condenser at a pressure of 75 kPa.

sg sl hg hl
Single phase at 3 MPa and 350oC: 6.745 - 3116.1 -
Double phase at 75 kPa: 7.456 1.213 2662.4 384.4

The quality of steam at the turbine exit:

a. 0.934 b. 0.845 c. 0.886 d .0.810

The thermal efficiency of the process:

a. 26% b. 34% c. 11% d. 64%
 PROBLEM 20
A nuclear power plant extracts 50 kg/s of saturated steam from the
reactor boiler such that it operates between pressures 100 kPa and 2
MPa. The water from the condenser is saturated and the steam exits
the turbine at a quality of 0.90.

P h(l), kJ/kg-K h(g) s(l) kJ/kg-K s(g)

0.1 MPa 417.3 2675 1.303 7.359
2.0 MPa 908.6 2798.3 2.45 6.34

The isentropic efficiency of the turbine is approximately:

a. 69% b. 87% c. 58% d. 95%

The plant efficiency is nearly:

a. 34.8% b. 14.5% c. 19.7% d. 17.3%
 PROBLEM 21
A vapor compression cycle using ammonia has an evaporator
temperature of 40degC and a condenser exit temperature of
30degC. What is the compressor power if the refrigerator has a
capacity of 50 tons:

Enthalpy at condenser: entrance = 1560 kJ/kg; exit = 341.769

kJ/kg
Enthalpy at evaporator: entrance = 341.76 kJ/kg; exit = 1407.26
kJ/kg
A. 25 kW C. 30 kW
B. 35 kW D. 40 kW
 PROBLEM 22
An ammonia simple saturation cycle operates with
a suction pressure of 291.6 kPa and a condenser
pressure of 1204 kPa develops 15 tons of
refrigeration. Determine the theoretical
horsepower of the compressor. The following
enthalpies have been found: condenser entrance =
1653 kJ/kg, exit = 346.6 kJ/kg; compressor entrance
= 1450.2 kJ/kg, exit = 1653 kJ/kg.

A. 7.23 hp B. 13 hp C. 15 hp D. 8.23 hp
 PROBLEM 23
The bubble point of a mixture containing 40%
methanol and 60% ethanol at 1 atm is nearly:

A. 75 degC
B. 72 degC
C. 65 degC
D. 82 degC
 PROBLEM 24
Compute the residual Gibbs energy, residual enthalpy and
actual pressure for nitrogen at STP.

Residual Gibbs, J/mol:

a. -1.09 b. -2.31 c. +1.43 d. +1.23 e. none

Residual Enthalpy, J/mol

a. -7.26 b. -9.21 c. +4.21 d. +1.24 e. none

Fugacity, Pa
a. 101, 276 c. 101,920 e. none
b. 102,323 d. 98,234