Integration of Heat Capacities

More ElaborateHeat Capacity Correlations for Wider Temperature

Ranges in 7th Edition of Perrys Chemical Engineering Handbook
Table 2-198 p.2-178-182

Cp=C1+C2(C3/T/(sinh(C3/T))2+C4(C5/T/cosh(C5/T))2
Temp in Degrees Kelvin
Cp Expressed in Joules/kmol/ oK

sinh(C3/T) = (e(C3/T) - e- (C3/T) )/2

cosh(C5/T) = (e(C5/T) + e- (C5/T) )/2

Refer to Table B.2 in Felder & Rousseau

(Form 1)CP= a +bT+CT2+dT3

(Form 2) Cp = a + bT +C/T2
Cp(Kilojoules/Mol/oK)

Be Careful about Interpreting Constant Correctly

from Felder & Rousseau

Compound state Form Temp ax103 bx105 cx108 dx1012

o
Acetone l 1 C 123.0 18.6
o
g 1 C 71.96 20.10 -12.78 34.76

CaO c 2 K 41.84 2.03 -4.52x1010

Cp(Acetone Liq) = 0.123+18.6x10-5T where T in oC

Cp(Acetone Gas) = 0.07196+20.10x10-5 T-12.78x10-8T2+34.76x10-12 T3

where T in oC
Cp(CaO Solid) = 0.04184+2.03x10-5 T +-4.52x102 T-2 where T in oK

Be careful with Cp (Liq Water)=75.4 x10-3KJ/mol/oC=75.4KJ/Kmol/oC

Other Heat Capacity Formulas

For Liquids & Solids (Cp & Cv) about the same

For Ideal Gases

Cp=Cv+R

Change in Specific Internal Energy

For Process Undergoing Change in Volume & Temperature

(T1 , V1 ) (T2 , V2 )

T2

U C v dT
T1

Exact for Ideal Gases

Good for Real Gases if Volume Constant
Good Approximation for Liquids & Solids
Change in Specific Enthalpy when T & P both Change

(T1,P1) (T2,P2)

Consider Two Step Path

(T1,P1)(T1,P2)(T2,P2)

For Ideal Gases

T2 T2 T2

H ( PV ) C p dT ( RT1 ) C p dT C p dT
T1 T1 T1

Also For Ideal & Real Gases if P Constant

T2

H C p dT
T1

However for Solids & Liquids

T2 T2

H ( PV ) C p dT VP C p dT
T1 T1
 Use of Kopps Rule to Approximate Heat Capacities
Refer to Perrys Handbook for Contributions of
Organic Functional Groups

Refer to Table B.10 (Atomic Heat Capacities)

Cpa (J/g-atom oC)
Element Solid Liquid
C 7.5 12
H 9.6 18
B 11 20
Si 16 24
O 17 25
F 21 29
P 23 31
S 26 31
All Others 26 33

Cp(SiO2 Solid)= 16+2*17 = 50 J/Mol/oC

Cp(SiO2 Liquid) = 24 + 2*25 = =74 J/Mol/oC

Enthalpy Changes of Mixtures of Gases or Liquids

50 Moles/hr
C10H22(Liq) Heater 50 Moles/hr
C10H22(Liq)
75Moles
C8H18(Liq) 75Moles C8H18
@25oC @80oC

80 80
H 50 C p ( DecaneLiq)dT 75 C p (Oc tan eLiq )dT
25 25

Key Assumption: Ignoring the Heat of Mixing

For Very Dilute Solutions (Based Heat Capacity on Solvent &
Ignore Solute
1 Mole
1 Mole Heater Octane(liq)
Octane(liq) 1000 Moles
1000 Moles Decane(liq)
Decane(liq) @80oC
@25oC

Calculation of Change in Enthalpy

80
H 1000 C p ( DecaneLiq )dT
25

Key Assumption: Neglect Heat of Mixing

Calculation of Heat Capacity of a Mixture &

Enthalpy Change for Mixture(Neglect Heat of Mixing)

(C p ) mix (T ) y i C pi (T )
i
T2

H (C p ) mix (T )dT
T1