Heat Effects

Chapter 4

Sensible Heat Effects, Latent Heats of Pure Substances,

Standard Heat of Reaction, Temperature Dependence of
∆Ho , Heat Effects of Industrial Reactions
 Importance of Heat Effects in Chemical Manufacturing Processes
Consider the process for the production of ethylene glycol by oxidation of
ethylene into ethylene oxide which is then dehydrated to glycol:
Air Water
25oC
Reactor
Ethylene
Preheater 25oC Ethyl
25oC Hydrator Glycol
(25-50oC) glycol
-Q
Sensible Heat Heat due to phase transition
Sensible Heat (Liquid → Solid)
+ Heat of Reaction
Heat effects include:
(1) Sensible heat: characterized by temperature change.
(2) Heat effects of chemical reactions
(3) Heat effects due to phase transition
(4) Heat of formation and separation of solutions
Calculation of heat evolved in each equipment is necessary for the design purposes.

Petroleum and Chemical Engineering Dept. Thermodynamics I 4-2

Sultan Qaboos University
 Sensible Heat Effects
It is the heat transfer to the system, or from the system, due to the temperature
change when there is no chemical reaction and no change in the composition
and no phase transition.
Objective: Develop a relation between heat transfer and the temperature change
 For pure homogeneous system, no change in composition:
U = U(T, V)
 U   U 
dU    dT    dV
 T   V 
 V  T
 U 
dU  CV dT    dV
 V 
 T Valid for:
 U 

 V
 dV  0
 when: (1) dV = 0 or (2) U ≠ U(V) (a) Ideal gas
 T
T2
(b) Incompressible
dU = CV dT U  
T1
CV dT fluid

Remember that for mechanically reversible constant-V process: Q = ∆U

Petroleum and Chemical Engineering Dept. Thermodynamics I 4-3

Sultan Qaboos University
 Similarly,
H = H(T, P)
 H   
dH    dT   H  dP
 T   P 
 P  T
 H 
dH  C PdT    dP
 P 
 T Valid for:
 H 
  dP  0
 P  when: (1) dP = 0 or (2) H ≠ H(P) (a) Ideal gas
 T
T2
(b) Low P gases
dH = C P dT H  
T1
C PdT

Remember that for mechanically reversible constant-P non flow process:Q = ∆H

Evaluation of ∫CP dT requires knowledge of temperature dependence of the
heat capacity.
In dimensionless: CP
= A + BT + CT 2 + DT -2
R

Petroleum and Chemical Engineering Dept. Thermodynamics I 4-4

Sultan Qaboos University
 ⇒ Thermodynamic properties are often accomplished in two steps:
 Calculate values for ideal-gas wherein ideal gas heat capacities are used,
 Correction of the ideal-gas values to the real-gas values is added.
Remember: a real gas becomes ideal gas as P → 0
For ideal gas, heat capacities are designated as: CigP and CigV and can be expressed as:
ig ig ig
CP where CV CP
= A + BT + CT 2 + DT -2 = -1
R R R
• The parameters A, B, C and D are tabulated for number of materials
• At low pressure, CigP ≈ CrgP
• Often CP for real gas is not too far from CP for ideal gas, thus it would be
logical to assume that C ig = C rg
P P
n
• For a gas mixture:
= ∑yi C P yi: mole fraction of each component
ig ig
Cmix i
i =1

Petroleum and Chemical Engineering Dept. Thermodynamics I 4-5

Sultan Qaboos University
 Example:
Calculate the heat required to raise the temperature of 1 mole of methane from 260
to 600oC in a flow process at a pressure sufficiently low ( ∼ideal gas).
For methane: A = 1.702 B = 9.08×10-3 C = -2.16×10-6 D = 0
T2 C Pig 873.14
Q  H  R  dT  (8.314) [1.702  9.08  10-3T -2.16  10-6T 2 ] dT
T1 R 533.15

(1.702)[873.15-533.15]  (9.083  10-3 / 2)[(873.15)2 -(533.15)2 ]

 (8.314)  -6 3 3


 -(2.16  10 / 3)[(873.15) -(533.15) ] 

 19.778 kJ

Petroleum and Chemical Engineering Dept. Thermodynamics I 4-6

Sultan Qaboos University
 Calculations involving sensible heat
• If T1 & T2 are known Straightforward calculations
• If ∆H is given and it is required to determine T2
Trial & error calculations
T2
H  R  (C P / R) dT  R [A(T2 -T1 )  (B / 2)(T22 -T12 )  (C / 3)(T23 -T13 )]
T1

For solving the resulting equation, rearrange so that T2 appears in the LHS ,
then solve for T2 and make LHS as calculated while the RHS as guessed one:
ΔH B 2 C
T2, calc = T1 + - (T2, guess - T12 ) - (T23, guess - T13 )]
AR 2 3

(See Example 4.3, p. 132)

Petroleum and Chemical Engineering Dept. Thermodynamics I 4-7

Sultan Qaboos University
 Matlab implementation
The function to be solved for T2:

H  B 2 C 3 3 
f (x )   2
- A(T2  T1 )  (T2  T1 )  (T2 -T1 )
R  2 3 
 

Define the function and then use the solver fsolve to solve for T2 starting
from an initial condition of T2=550K. In this case C=0.

F='(37218/8.314) - (3.578*(x - 533.15) + (3.02e-3/2)*(x^2 - 533.15^2))';

x=fsolve (F,550)

Petroleum and Chemical Engineering Dept. Thermodynamics I 4-8

Sultan Qaboos University
 Latent Heat of Pure Substances

Vaporization, or condensation, fusion or solidification, occur at constant

temperature and pressure. However, these processes require the transfer of certain
amount of heat to or from the substance. Latent Heat
Solid → Liquid ⇒ Latent heat of fusion (melting)
Liquid → vapor ⇒ Latent heat of vaporization (evaporation)
 Energy evolved upon separation or combining molecules together during the
phase transition process

Fusion (melting) Vaporization

Solid Liquid Vapor
Solidification Condensation

Petroleum and Chemical Engineering Dept. Thermodynamics I 4-9

Sultan Qaboos University
 Methods for Determination of Latent Heat
(1) Use of P-V volumetric data
 These processes are characterized by the coexistence of two phases.
 Latent heat accompanying a phase transition is a function of T only and
can be determined using the following relation:
dP sat
ΔH = TΔV
dT T2 < T1 < Tc < T

∆H = latent heat;
∆V = volume change accompanying the phase change;
Psat = vapor pressure
dPsat/dT and ∆V can be calculated from the P-T relation
and volumetric data, respectively. Psat

B
Antoine Equation: ln P sat = A +
T +C T

Petroleum and Chemical Engineering Dept. Thermodynamics I 4-10

Sultan Qaboos University
 (2) Use of Calorimeteric data
 ∆H can be determined experimentally (calorimetrically)
 Results are normally represented by certain correlations which are available in
literature

If point 1, the reference point (T1, P1) enthalpy assigned to be Ho = 0;

⇒ At point 2, T = T2, according to the first law:
Q = H2

Petroleum and Chemical Engineering Dept. Thermodynamics I 4-11

Sultan Qaboos University
 (3) Approximate Methods
Often, ∆H is not available at the temperature of interest. Thus, approximate
methods serve two purposes:
a. Prediction of ∆Hvap at normal boiling point Tn (i.e. at 1 atm)
b. Estimation of ∆Hvap at any temperature from the known value at certain temp.

ΔH n / Tn 1.092(ln Pc - 1.013) Riedel equation

= Valid for any substance
R 0.93 - Trn

Tn = normal boiling point; ∆Hn = molar heat of vaporization at Tn

Pc = critical pressure; Trn = reduced temperature at Tn (Trn = Tn/Tr)

At any other temperature, T2, latent heat of vaporization, ∆H2, can be determined
based on the known latent heat, ∆H1, at temperature T1:
0.38
H 2  1-T  Watson equation
 
r2 

H 1  1-Tr1  Valid for any substance
See example 4.4

Petroleum and Chemical Engineering Dept. Thermodynamics I 4-12

Sultan Qaboos University
 Standard Heat of Reaction
 So far heat was evolved due to physical changes only.
 Chemical reactions are accomplished either by the transfer of heat (exothermic
or endothermic reactions) or by temperature changes during the course of
reaction.
 In chemical reactions, heat is evolved due to the difference in the molecular
structure between products and reactants, i.e. different levels of energy

Example: Reactants in combustion reactions possess greater energy based on

their structure than do the products:
Reactants Products
High energy +Q Low energy
 To reduced the number of possible data for heat of reaction,
reactions can be carried out at standard conditions.

 For consistent treatment of reactions, heat effects can be done

when both reactants and products are all at the same temperature.

Petroleum and Chemical Engineering Dept. Thermodynamics I 4-13

Sultan Qaboos University
 Standard Heat of Reaction
For purpose of tabulation, consider the following reaction:
aA + bB cC + dD
Standard heat of reaction: The enthalpy change when a moles of A and b moles of B
react to form c moles of C and d moles of D at their standard states at temperature T.
Standard state: a particular state of a species at specification of T, P, composition
and physical state Standard, designated as “o”

• Gases: Pure substance in the ideal gas state at 1 bar.

• Liquids & Solids: Actual pure liquid or solid at 1 bar.
ig
C Po : Standard-state heat capacity (C Po = C P ) listed in Table C-1

 All conditions at standard state are fixed except T, i.e. standard state = f(T)
o
Example: ½ N2 + 3/2 H2 → NH3 H 298  -46110 J Check using Table C-4

Doubling the stoichiometry ⇒ ∆H should be doubled

N2 + 3 H2 → 2 NH3 H 298o
 -92220 J

Petroleum and Chemical Engineering Dept. Thermodynamics I 4-14

Sultan Qaboos University
 Standard Heat of Formation
 Tabulation of data for standard heat of all possible reactions is impossible
 Standard heat of formation of the component would be more practical
Formation reaction: a reaction which forms a single compound from its
constituent elements
C + ½ O2 → CH3OH Formation reaction
H2O + SO4 → H2SO4 Not formation reaction
• Formation reaction is based on 1 mole of compound, i.e. heat per 1 mole
of compound
• Heat of reaction at any temperature can be calculated if it is known at any
other temperature
Heat of formation is tabulated at 25oC, designated as ΔH of , 298
(See Table C.4, App. C)
ΔH of , 298 Can be added for each component in the reaction to give the
standard heat of the desired reaction
• Heat of formation for pure element is assigned as zero in order to determined ∆Hof,298
Petroleum and Chemical Engineering Dept. Thermodynamics I 4-15
Sultan Qaboos University
 For a given reaction, heat of reaction can be calculated based on the heat of
formation for each compound in the reaction using the following formula:
ΔH Ro = ∑
Products
ΔH of ,i - ∑
Reactants
ΔH of ,i

Example: Calculate the heat of reaction at 25oC for the following reaction:
CO2 (g) + H2 (g) CO (g) + H2O (g)
Heat of formation are given for each compound:
Reactants Products
CO2: ΔH of , 298 = -393509 J/mol CO: ΔH of , 298 = -110525 J/mol
H2: ΔH of , 298 = 0.0 H2O: ΔH of , 298 = -241818 J/mol

ΔH Ro , 25 C = (ΔH of ,CO, 298 + ΔH of ,H O, 298 ) - (ΔH of ,CO

o
2 2 , 298
+ ΔH o
f ,H 2 , 298 )

= (-241818-110525)-(-393509)
= 41166 J/mol

Petroleum and Chemical Engineering Dept. Thermodynamics I 4-16

Sultan Qaboos University
 Temperature Dependence of ∆Ho
∆H o
0

Objective: Calculation of standard heats of reaction at a certain

temperature from the knowledge of heat of reaction at a reference
temperature ( ΔH 0o ).
Consider the following general chemical reaction:
ν 1 A1 + ν 2 A2 + ⋅ ⋅ ⋅ ⋅ ⋅ → ν 3 A3 + ν 4 A4 + ⋅ ⋅ ⋅

|νi| is the stoichiometric coefficient ⇒ |νi| +ve for products

|νi| −ve for reactants
νi itself is called the stoichiometric number
Example: N + 3H → 2 NH
2 2 3

⇒ νN2 = -1; νH2 = -3; νNH3 = 2

Thus, in terms of the stoichiometric number , the standard heat of

reaction can be expressed as:

Petroleum and Chemical Engineering Dept. Thermodynamics I 4-17

Sultan Qaboos University
 ∆H o ≡ ∑ vi H io
i
Where Hio is the enthalpy of species i in its standard state which is equals
to the standard heat of formation, that is:

H io ≡ ∆H of i
⇒ ∆H o ≡ ∑ vi ∆H of i
i
Example:
4 HCl ( g ) + O2 → 2 H 2O ( g ) + 2Cl2 ( g )
From Table C.4 at 298.15 K
⇒ ∆H = o
2 ∆H ofH O − 4 ∆H ofHCl
2
Species
vi ∆H ofi
∆H 298
o
= ( 2)( −241,818) − ( 4)( −92,307)
HCl (g) -4 -92,307
= −114,408 J
O2 -1 0.0
H2O (g) 2 -241,818
Cl2 2 0.0

Petroleum and Chemical Engineering Dept. Thermodynamics I 4-18

Sultan Qaboos University
 For any species, i, enthalpy is function of T and P, but at constant P
the change of enthalpy for species i due to change in T can be
expressed as
dH i = C P dT
i

Thus, in the standard-state, since P is fixed, this can be written as:

dH io = C Po dT i

Multiplying by νi ⇒ ν i dH io = ν i C Po dT
i

Summing over all components ⇒ ∑ν i dH i = ∑ν i C P dT

o o
i

( )
i i
LHS = ∑ν i dH io = ∑ d ν i H io =d ∑ν i H io = d∆H o ∆H o ≡ ∑ vi H io
i i i i
 
( ) ∆ C Pi i
0
 =R C
RHS = ∑ ν i C Pi i dT =RdT ∑ ν i P
dT
 
R  R
i i 
∆C P0  C Pi 
= ∑ ν i i 
where: R  R
i 



Petroleum and Chemical Engineering Dept. Thermodynamics I 4-19

Sultan Qaboos University
 ∆C Po
Since LHS = RHS ⇒ d∆H = R
o
dT
R
Integrating:
∆H o ∆C PoT T ∆C Po
∫∆H 0o d∆H = R ∫T0 R dT ⇒ ∆H o = ∆H 0o + R ∫
o
dT
T0 R
Calculations involve the following steps:
1. Calculate heat of reaction at the reference temperature, T0 ⇒ ∆H0o
 C Pi 
∆
( ( ))
0
C  = ∑ ν i Ai + BiT + CiT 2 + DiT −2
2. Determine: P
= ∑ ν i i

R  R  i
i  
       
=  ∑ν i Ai  +  ∑ν i Bi T +  ∑ν i Ci T 2 +  ∑ν i Di T −2
 i   i   i   i 
= ∆A + ∆BT + ∆CT 2 + ∆DT −2
3. Perform the integration
4. Multiply the integration results by R and add the result to step 1.

Petroleum and Chemical Engineering Dept. Thermodynamics I 4-20

Sultan Qaboos University
 Example 4.6
Calculate the standard heat of the methanol-synthesis reaction at 800oC:
CO ( g ) + 2 H 2 ( g ) → CH 3OH ( g ) Table of data
∆H 0o = ∆H 298
o
= ∑ν i ∆H of i , 298
i νi ∆ H o A 103 B 106 C 10-5 D
f i , 298
CH3OH 1 -200,660 2.211 12.216 -3.450 0.000
= −200,660 − ( −110,525)
CO -1 -110,525 3.376 0.557 0.000 -0.031
= −90,135 J H2 -2 0.0 3.249 0.422 0.000 0.083

Calculation of the constants:

∆A = ∑ν i Ai = (1)( 2.211) + ( −1)(3.376) + ( −2)(3.422) = −7.663
i
Similarly: ∆B = 10.815 × 10-3 ∆C = -3.45 × 10-6 ∆D = -0.135 × 105
Perform the integration:
1073.15
T C Po
T0 R
dT   7.663  10.815  103T  3.45  106  0.135  105T 2dT = -1615.5 K
298.15

∆Ho = -90135+8.314(-1615) = 103566 J

Petroleum and Chemical Engineering Dept. Thermodynamics I 4-21

Sultan Qaboos University
 Problem 4.21(f) & 4.23
Calculate the standard heat of reaction at 25oC and at 650oC for the reaction:

6 NO2 ( g ) + 8 NH 3 ( g ) → 7 N 2 ( g ) + 12 H 2O ( g )
Table of data (from C.1)
∆H 0o = ∆H 298
o
= ∑ν i ∆H of i , 298
i νi ∆ H of A B
i , 298
= (12)( −241818) + (7)(0) H2O (g) 12 -241818 3.47 0.00145
− (8)( −46110) − (6)(33180) N2 (g) 7 0.0 3.28 0.00593
= −2732016 kJ NH3(g) -8 -46110 3.578 0.00302
NO2 (g) -6 33180 4.982 0.00119
Calculation of the constants:
∆A = ∑ν i Ai = (12)(3.47) + (7)(3.28) + (−8)(3.578) + (−6)(4.982) = 6.148
i
Similarly: ∆B = 0.002761
Perform the 923.15
T ∆C o
integration: ∫ T0 R
P dT =
∫
6.148 + 0.002761T dT = 24894 K
298.15
∆Ho = -273201 + 8.314(24894) = -2525.0 kJ

Petroleum and Chemical Engineering Dept. Thermodynamics I 4-22

Sultan Qaboos University
 Industrial Reactions

 Industrial reactions are carried out under standard-state

conditions.
 Actual reactions may not present in stoichiometric proportions.
 Reactions may not go to completion.
 Products temperature might be different that reactant temperature.
 Inerts may present.

⇒ Each reaction requires special treatment.

Petroleum and Chemical Engineering Dept. Thermodynamics I 4-23

Sultan Qaboos University
 Example: Combustion reaction
What is the maximum temperature that can be reached by the combustion of
methane with 20% excess air? Both the methane and the air enter the burner
at 25oC. CO
CH4 2

T=25oC CH 4 + 2O2 → CO2 + 2 H 2O ( g ) H2O

20% excess O2 Tmax ?

i νi ∆H of A B 10-5 D ni, exit

i , 298
(mole)
CH4 -1 -74520 1.702 0.009081 0.0 0.0
O2 -2 0.0 3.639 0.5060 -0.227 0.4
CO2 1 -393509 5.457 1.045 -1.157 1.0
H2O (g) 2 -241818 3.470 1.450 0.121 2.0
N2 inert 0.0 3.280 0.593 0.040 9.03

o
∆H 298 = ∑ν i ∆H of i , 298
= ( −1)( −74520) + ( −2)(0) + (1)( −393509) + ( 2)( −241818) = −802,625 J
i

Petroleum and Chemical Engineering Dept. Thermodynamics I 4-24

Sultan Qaboos University
 Assume combustion is complete and adiabatic:
Q = 0.0 ⇒ ∆Ho = 0.0
Product
Since enthalpy is a state function then assume the two paths: @ 1 bar
&T
1. Reaction occurs at 25oC to form the product
2. Products are heated to T 1 mol CO4
∆H o = H 298
o
+ ∆H oprod = 0.0 2 mol H2O
0.4 mol O2
9.03 mol N2
Material balance: Assume basis 1 mole CH4 ∆H oprod
Moles O2 required = 2 moles
Moles O2 in excess = 2(0.2)=0.4 moles Const. T (25oC)
Product
Moles of N2 in = 2.4(79/21)=9.03 moles Reactant ∆H ofi , 298
@ 1 bar & 25oC
T ∆C o 1 mol CH4
∫
o
∆H P = P dT 2.4 mol O2
T0 R 9.03 mol N2

∑n ( A + BT + C T + DiT −2 )
o o
∆CP
∑ =
CP ,i 2
where = ni ,exit i , exit i i i
R R i
i
T ∆C o T      
o
∆H P = ∫
T0 R
P dT = 
298 ∫ ∑ 
ni Ai +
 

∑
ni Bi T +


  ∑
ni Di T − 2 dT
 i   i   i 

Petroleum and Chemical Engineering Dept. Thermodynamics I 4-25

Sultan Qaboos University
 T
= 43.47 + 0.0095T − 0.0645 × 105T − 2 dT
∫298
since ∆H o = H 298
o
+ ∆H oprod = 0.0

 1 1 1 
∴ 0.0 = −802626 + 8.314 43.47(T − 298) + (T 2 − 2982 ) + 0.0645 × 105  − 
 2  T 298 

Solve for T by trial and error procedure, to get:

T = 2066 K

Petroleum and Chemical Engineering Dept. Thermodynamics I 4-26

Sultan Qaboos University
 Example 4.8: Catalytic reforming
Catalytic reforming of CH4 with steam occurred according to the
following reaction:
CH 4 ( g ) + H 2O ( g ) → CO ( g ) + 3H 2 ( g ) ∆H 298
o
= 205,813 J (1)
CH 4 ( g ) + 2 H 2O ( g ) → CO2 ( g ) + 4 H 2 ( g ) ∆H 298
o
= 164,647 J (2)

 2 moles of steam entered the reactor for each mole of CH4.

 Heat supplied to the reactor for a product temperature of 1300 K.
 CH4 is completely converted.
 Product stream contains 17.4 mol-% CO.

If the reactants are at 600oC, calculate the heat requirement for the
reactor.

Petroleum and Chemical Engineering Dept. Thermodynamics I 4-27

Sultan Qaboos University
 Solution (Ex.:4.8)
CH 4 ( g ) + H 2O ( g ) → CO ( g ) + 3H 2 ( g )
-x -x x 3x

CH 4 ( g ) + 2 H 2O( g ) → CO2 ( g ) + 4 H 2 ( g )
-(1-x) -2(1-x) (1-x) 4(1-x)
Solution: Material balance to determine the constituents of the feed and the
product streams
Assume a basis of 1 mol CH4 and 2 mold H2O fed to the reactor
Let x be mol of CH4 reacts by rxn 1 ⇒ (1- x) is mol of CH4 reacts by rxn 2
⇒ Moles of product: CO: x
H2: 3x + 4(1-x) = 4-x
CO2: 1- x mole fraction of CO=0.174=x/5
H2O: 2-x-2(1-x) = x ∴ x = 5(0.174) = 0.87 mol
⇒ Total = 5 mol product

Petroleum and Chemical Engineering Dept. Thermodynamics I 4-28

Sultan Qaboos University
 600 K 1300 K
Re-calculate moles of product as Reactor
summarized ⇒ 1 mol CH4
CO: 0.87
H2: 3.13
2 mol H2O
CO2: 0.13
Q = ∆Ho H2O: 0.87
Products
Since heat of reactions is available only at 298 ⇒ proper 1 bar & 1300 K
path for ∆Ho should be selected ∆Ho 0.87 mol CO
3.13 mol H2
Reactants 0.13 mol CO2
o o o o
 H  H  H R 298
 H P ∆H Po 0.87 mol H2O
1 bar & 600 K
1 mol CH4 ∆H Ro
2 mol H2O
∆H 298
o
Product
298 K

o o o
For RxN 1: H 298  x H 298, 1
 (1  x ) H 298, 2
(x) moles CH4 reacts =0.87 mole
 (0.87)(205, 813)  (0.13)(164647)
For RxN 2:
(1-x) moles CH4 reacts =0.13 mole = 200, 460 J

Petroleum and Chemical Engineering Dept. Thermodynamics I 4-29

Sultan Qaboos University
 ∆CPo , R 298    
∑ ∑
T0
∆H ∫TR R
R= ∫600  i i,R i   i i,R i  T dT
+
o
R dT R n A n B

  i ni,R ni,P A B
 ∑ ni , R Ai  = (1)(1.702) + ( 2)(3.47) = 8.642 CH4 1.0 0.0 1.702 9.081
 i 
  H2O 2.0 0.87 3.470 1.450
 ∑ ni , R Bi  = (1)(9.08) + ( 2)(1.45) = 11.94 CO 0.0 0.87 0.337 0.557
 i 
H2 0.0 3.13 3.250 0.422
298
∴ ∆H Ro == R ∫ 8.642 + 11.98T dT = −34,390 J 2 CO 0.0 0.13 5.450 1.045
600
TP ∆C P , P 1300    
o

∫T0 R
∆H Po R= dT R ∫298  ∑i i,P i   ∑i i,P i  T dT
n A + n B
 



∑ ni , P Ai

 = (0.87)(3.47) + (0.87)(0.337) + (3.13)(3.25) + (0.13)(5.45) = 14.19

 i 
 



∑ ni , P Bi

 = (0.87)(1.45) + (0.87)(5.57) + (3.13)(0.422) + (0.13)(1.045) = 7.53

 i  1300
∴ ∆H Po == R ∫ 298
14.19 + 7.53T dT = 161940 J
∆Ho = Q = -34390 + 200460 + 161940 = 328 kJ

Petroleum and Chemical Engineering Dept. Thermodynamics I 4-30

Sultan Qaboos University
 Assignment

 Solve the following problems from your

textbook:
 4.13
 4.18
 4.44

Petroleum and Chemical Engineering Dept. Thermodynamics I 4-31

Sultan Qaboos University
 Clapeyron Equation
dP sat
ΔH = TΔV
 The Clapeyron equation is expressed as: dT
RT
 At relatively low pressures: ΔV = Vg − Vl ≅ Vg ΔV =
P
RT 2 dP sat
 Hence the Clapeyron equ. Can be put as: ΔH =
P dT

 Separation of variables and integrating gives:

P2  dP 
sat
T2 ∆H  dT 
sat
P ∆H 1 1
=  − 
∫ P1 
 P 
 =∫
T1  
R  T2 
ln 2
P1 R  T2 T1 

 This is the Clapeyron equation at relatively low pressures.

Petroleum and Chemical Engineering Dept. Thermodynamics I 4-32

Sultan Qaboos University