Source: Equations and examples adopted from Smith, J.M., Van Ness, H.C. and Abbott, M.M.

Introduction to Chemical Engineering Thermodynamics, 7th Edition, McGraw-Hill, 2005(if not specified elsewhere)

Chapter 4: Heat Effects

Heat transfer is common in chemical industry. Combustion, extraction, distillation etc. involve heat effects that accompany physical and chemical changes with the principle of thermodynamics.

Objective

To apply thermodynamics to the evaluation of the heat effects that accompany physical and chemical operations

Sensible heat effects (temperature change) Latent heat effects (phase transition) Heat effects of chemical reaction, formation, and combustion under standard conditions as well as actual industrial conditions Heat effects of mixing processes (not treated in this chapter)

Sensible Heat Effects

Relations between quantity of heat transferred and resulting temperature change

For mechanically reversible, constant-volume, closed-system processes

Q = U = CV dT
T1

T2

For mechanically reversible, constant-pressure, closed-system processes / steady-flow heat transfer where EP , EK 0, Ws = 0

Q = H = C P dT
T1

T2

Sensible heat effects are characterised by temperature changes in a system in which there are no phase transitions, no chemical reactions, and no changes in composition.
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Heat Capacity:Temperature Dependence

ig

CP 2 2 = A + BT + CT + DT R

ig Ideal-gas heat capacity, C P rather than actual heat capacity

More convenient for thermodynamic-property evaluation in two steps:

1.

2.

Calculation for hypothetical ideal-gas-state values Correction to real-gas values

Parameters in equation for CP can be found in App. C.

Relations between the two ideal-gas heat capacities

ig ig CV CP = 1 R R

Heat Capacity: Gas Mixtures

ig ig ig ig C Pmix = y A C PA + y B C PB + y C C PC + ...

ig C Pmix =

ig y i C Pi

In an ideal-gas mixture, the molecules have no influence on one another, and each gas exists independent of the others.
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Heat Capacity: Evaluation of the Integral

T T ig P

C Q = H = C P dT = R dT T0 T0 R

To calculate Q or H given T0 and T:

Read textbook, Smith et al. (2005) p.130 and Ex. 4.2 for details.

Heat Capacity: Evaluation of the Integral

To calculate T given T0 and Q or H (an iteration scheme is helpful):

1. Guess T, then calculate , then substitute into Eq. (4.8)

H

H = C P

(T T0 )

2. Substitute <CP>H into Eq. (4.10) to get new T

H T= + T0 CP H

(4.10)

3. Substitute new T into Eq. (4.8) to reevaluate <CP>H until iteration converges.
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Read textbook, Smith et al. (2005) p.130 for details.

Exercise: Problem 4.2 (a)

For steady flow through a heat exchanger at approximately atmospheric pressure, what is the final temperature, (a) when heat in the amount of 800 kJ is added to 10 mol of ethylene initially at 200C (473.15 K)?

103 B = 14.394 B = 14.394 x 10-3

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Exercise: Problem 4.2 (a) (contd)

Guess T = 400C (673.15 K), thus = 2.

CP

R CP

14.394 10 3 4.392 10 6 (473.15)(2 + 1) + (473.15)2 22 + 2 + 1 + 0 = 1.424 + 2 3

= 9.346

H T= + T0 CP H

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Latent Heats of Pure Substances

Phase transition, coexistence of two phases, no temperature change Clapeyron equation (derived in Chapter 6)

dP sat H = TV dT

Troutons rule (rough estimates at Tn) H n 10 RTn

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Latent Heats of Pure Substances

H n 1.092(ln Pc 1.013) = RTn 0.930 Trn
P (bar)

Riedel equation (high accuracy, error < 5%)

Watson equation (with a known value, experimental or estimated by Riedel equation)

H 2 1 Tr2 = H1 1 Tr1

0.38

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Standard Heats: Reaction, Formation, Combustion

Revision: Read Chapter 4 (4.3-4.5), Smith et al. (2005)

H o vi H o fi
i

Positive (+) for products Negative () for reactants

Standard states: pure substance at ideal-gas state at 1 bar, real pure liquid or solid at 14bar 1

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Standard Heats:Temperature Dependence

temperature change

temperature change

chemical reaction

16

Standard Heats:Temperature Dependence

17

Standard Heats:Temperature Dependence

18

Example 4.6: Standard heat at temperature other than 298.15 K

Calculate standard heat of methanol-synthesis reaction at 800C (1073.15 K):

CO(g) + 2H2(g)

CH3OH(g)

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Ai = A

20

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Heat Effects of Industrial Reactions

Industrial reactions are often carried out under/with

non standard-state conditions non stoichiometric proportions reaction not go to completion variation in temperature presence of inert several reactions simultaneously

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Conclusions

In this chapter, we have evaluated the heat effects that accompany physical and chemical operations from the point of thermodynamics. We have examined

Sensible heat effects (as a result of temperature change) Latent heat effects (due to phase transition) Heat effects of chemical reaction, formation, and combustion under

standard conditions actual industrial conditions

Self study
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Read Chapter 4 (Smith et al. 2005) Attempt Tutorial 3: Problems 4.11, 4.38, 4.49,4.51