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Concerned

with energy changes and


energy flow in a chemical process.
Conservation of energy first law of
thermodynamics i.e. accumulation of
energy in a system = energy input
energy output

Forms of energy

Potential energy (mgh)


Kinetic energy (1/2 mv2)
Thermal energy heat (Q) supplied to or removed
from a process
Work energy e.g. work done by a pump (W) to
transport fluids
Internal energy (U) of molecules

m mass (kg)
g gravitational constant, 9.81 ms-2
v velocity, ms-1

Energy balance
W

mass in

mass out
system

Hin

Hout
Q

IUPAC convention
- heat transferred to a system is +ve and
heat transferred from a system is ve
- work done on a system is+ve and work
done by a system is -ve

Steady state/non-steady state


Non

steady state accumulation/depletion of energy in


system

Uses

Heat required for a process


Rate of heat removal from a process
Heat transfer/design of heat exchangers
Process design to determine energy requirements of a
process
Pump power requirements (mechanical energy balance)
Pattern of energy usage in operation
Process control
Process design & development
etc

Enthalpy balance
p.e.,

k.e., W terms = 0
Q = H2 H1 or Q = H
, where H2 is the total enthalpy of output
streams and H1is the total enthalpy of
input streams, Q is the difference in
total enthalpy i.e. the enthalpy (heat)
transferred to or from the system

continued
Q

ve (H1>H2), heat removed from


system
Q +ve (H2>H1), heat supplied to
system.

Enthalpy changes
Change

of T at constant P
Change of P at constant T
Change of phase
Solution
Mixing
Chemical reaction
crystallisation

Latent heats (phase changes)


Vapourisation

(L to V)
Melting (S to L)
Sublimation (S to V)

Mechanical energy balance


Consider mechanical energy terms only
Application to flow of liquids
P + v2 + g h +F = W

2
where W is work done on system by a pump
and F is frictional energy loss in system (J/kg)
P = P2 P1; v2 = v22 v12; h = h2 h1

Bernoulli equation (F=0, W=0)

Sensible heat/enthalpy
calculations

Sensible heat heat/enthalpy that must be transferred


to raise or lower the temperature of a substance or
mixture of substances.
Heat capacities/specific heats (solids, liquids,
gases,vapours)
Heat capacity/specific heat at constant P, Cp(T) = dH/dT
or H = integral Cp(T)dT between limits T2 and T1
Use of mean heat capacities/specific heats over a
temperature range
Use of simple empirical equations to describe the
variation of Cp with T

continued
e.g. Cp = a + bT + cT2 + dT3
,where a, b, c, d are coefficients
H = integralCpdT between limits T2, T1
H = [aT + bT2 + cT3 + dT4]
2
3
4
Calculate values for T = T2, T1 and subtract
Note: T may be in deg cent or K - check units for Cp!

Heat capacity/specific heat data

Felder & Rousseau pp372/373 and Table B10


Perrys Chemical Engineers Handbook
The properties of gases and liquids, R. Reid et al, 4th
edition, McGraw Hill, 1987
Estimating thermochemical properties of liquids part
7- heat capacity, P. Gold & G.Ogle, Chem. Eng.,
1969, p130
Coulson & Richardson Chem. Eng., Vol. 6, 3rd edition,
ch. 8, pp321-324
PhysProps

Energy balances on systems


involving chemical reaction

Standard heat of formation (Hof) heat of


reaction when product is formed from its
elements in their standard states at 298 K, 1
atm. (kJ/mol)

aA + bB
cC + dD
-a-b +c +d (stoichiometric coefficients, i)
HofA, HofB, HofC, HofD (heats of formation)
HoR = c HofC + d HofD - a HofA - bHofB

Heat (enthalpy) of reaction


HoR

ve (exothermic reaction)

HoR

+ve (endothermic reaction)

Enthalpy balance equation reactor


Qp = Hproducts Hreactants + Qr
Qp heat transferred to or from process
Qr reaction heat ( HoR), where is
extent of reaction and is equal to [moles
component,i, out moles component i,
in]/ i

Hreactants

Hproducts
system
Qr
+ve

Qp
-ve
Note: enthalpy values must be calculated with reference to a
temperature of 25 deg cent

Energy balance techniques

Complete mass balance/molar balance


Calculate all enthalpy changes between
process conditions and standard/reference
conditions for all components at start (input)
and finish (output).
Consider any additional enthalpy changes
Solve enthalpy balance equation

Energy balance techniques


Adiabatic

temperature: Qp = 0

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