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 Acetone

state l g c

Form Temp ax103 bx105 cx108 1 1 2

o o

dx1012

C C

123.0 18.6 71.96 20.10 -12.78 41.84 2.03 -4.52x1010

34.76

CaO

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

) (T , V ) (T1 , V 1 2 2

C dT U v
T1

T2

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

( PV ) C dT ( RT ) C dT C dT H 1 p p p
T1 T1 T1

T2

T2

T2

Also For Ideal & Real Gases if P Constant

C dT H p
T1

T2

However for Solids & Liquids

( PV ) C dT V H p P C p dT
T1 T1

T2

T2

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

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

25 25

80

80

Key Assumption: Ignoring the Heat of Mixing

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

Calculation of Change in Enthalpy

H 1000 C p ( DecaneLiq)dT
25 80

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 ) H
T2

yC
i i

pi

(T )

(C

) mix (T )dT

T1