Energy Balances for Systems with Chemical Reactions Start with Himmelblau & Riggs (7th ed), p. 660.

Et2 t1 = U t2 + PEt2 + KEt2 U t1 + PEt1 + KEt1

) (

(1)

Et2 t1 = Q + W + U in + PE in + KE in min U out + PE out + KE out mout + Pin V in min Pout V out mout

(2)

W is work, other than PV work, done by the surroundings on the system. Pin V in min is the PV work done on the system in order to "push" the volume V in min into the system at pressure Pin and where the carat above V means per unit mass Consider systems where changes in PE and KE are negligible
Et2 t1 = U t2 t1 = Q + W + U in + Pin V in min U out + Pout V out mout

(3) (4)

U t2 t1 = Q + W + H in min H out mout

Divide by t and take the limit as t 0

dU = Q + W + H in min H out mout dt

(5)

where the dots above Q, W and m make them rates. For reactions, it is convenient to use molar flow rates, Fi, rather than mass flow rates:

dU = Q + W + Fi ,in H i ,in Fi ,out H i ,out dt dU ' ' = Q + W + Fi ,in ( H i ,in H i ,out ) + H rxn in out dt

(6)

(7)

where ' is the stoichiometric extent of reaction for a single reaction system with units (mol/s), and where the sums are over all the species. The enthalpy change by reaction, the "heat of reaction" at outlet T is
H rxn = i H f ,i

(8)

where i is the formal stoichiometric coefficient of species i, and H f ,i is the enthalpy of formation of species i at outlet T. Think of the next to last group on the righ-hand-side (RHS) as the enthalpy change to take the feed from inlet T to outlet T, and the last group on the RHS as the enthalpy change due to the change in composition by reaction at T. The next to the last group on the RHS can be expressed in terms of the molar heat capacity of the inlet fluid per mole of species A and the temperature difference.

dU ' ' = Q + W + FA,inCP ,in (Tin Tout ) + H rxn in out dt

(9)

At steady state, the energy balance and material balance for a single reaction system are:

dU ' ' = 0 = Q + W + FA,in CP ,in (Tin Tout ) + H rxn in out << energy balance dt d ' ' = 0 = in out rAV dt
<< steady-state material balance

(10)

(11)

Combining Equations 10 and 11,

0 = Q + W + FA,inCP ,in (Tin Tout ) + H rxn rAV

(12)

which can also be written in the following, equivalent way

0 = Q + W + FA,inCP ,in (Tin Tout ) + ( H rxn )( rAV )

(13)

Now consider un-steady state conditions. Expand dU

U U U dU = d + dT + dP T P , P T , T , P

(14)

where is the stoichiometric extent of reaction for a single reaction system with units (mol). The last group on the RHS of Equation 14 is usually negligible, and is zero at constant pressure. Specify constant mass m in the system, neglect the last term, and divide by dt to get
dU U dT U d = + dt T P , dt T , P dt

(15)

Looking at the groups on the RHS:

dT dT U dT = N i CPi = N tot CP dt T P , dt dt

(16)

where CP is the average molar heat capacity of the fluid in the system and N tot is the total moles in the system.
U = H rxn T , P

(17)

where H rxn is the "heat of reaction" per mole of reactant whose formal stoichiometric coefficient i = -1. A material balance for a single reaction system gives

d ' ' = in out rAV dt

for reactant species A whose formal stoichiometric coefficient A = -1. Combining Equations 15-18

(18)

dU dT ' ' = N tot CP + H rxn (in out rAV ) dt dt

Substituting Equation 19 into Equation 9 above, we get

(19)

N tot CP

dT ' ' ' ' + H rxn (in out rAV ) = Q + W + Ftot ,inCP ,in (Tin Tout ) + H rxn (in out ) (20) dt dT = Q + W + Ftot ,inCP ,in (Tin Tout ) + H rxn rAV dt dT = Q + W + Ftot ,inCP ,in (Tin Tout ) + ( H rxn )( rAV ) dt
(21)

N tot CP

N tot CP

(22)

Note that, for an un-steady state system, the last group on the RHS now also includes the contribution to energy accumulation in the system due to changes in the composition of the fluid in the system. The left-hand side now accounts for the energy accumulation in the system due only to the change in temperature. Note that N tot and CP , as defined by

Equation 16, can change with time due to changes in volume of fluid and composition of fluid in the system. Also see the derivation in Fogler (4th ed), pp. 591-593. Compare Equation 22 to Fogler (4th ed), p. 593, Equation 9-10:

N A0CPs

dT = Q Ws + FA0CPs (Tin Tout ) + ( H rxn )( rAV ) dt

(23)

where CPs is the average heat capacity of the solution per mole of species A. Note the different sign convention on work: the work W above and in Himmelblau & Riggs = - Ws in Fogler. That is, positive work in Himmelblau & Riggs is work done on the system (H&R, 7th ed, p. 614), whereas in Fogler, positive work is work done by the system (Fogler, 4th ed, p. 473). Defining an average heat capacity per unit mass, CPm , we can write the energy balance as

VCP

dT = Q + W + vCPm (Tin Tout ) + ( H rxn )( rAV ) dt

(24)

REFERENCES D. M. Himmelblau and J. B. Riggs, "Basic Principles and Calculations in Chemical Engineering," 7th ed., Prentice Hall (2004). H. S. Fogler, "Elements of Chemical Reaction Engineering," 4th ed., Prentice Hall (2006).