Energy Balances

2 lectures + 1 tutorial
Dr John Christy

Energy Balances
Relates energy (enthalpy) content and
flowrates of process streams
Principle: Conservation of energy
Enthalpy is the energy due to motion of
molecules and their constituent parts plus
the energy available to cause fluid flow.
Enthalpy depends on conditions of state
(T, P, composition, phase)

Energy Balances

Equations
Input of _ output of = accumulation of
Energy
Energy
energy in process
NB. No generation or consumption terms.
Steady state: accumulation = 0
rate energy input = rate energy output
Rate in = i fi,in.(hi,in + pei,in + kei,in) + Q + W
Rate out = i fi,out.(hi,out + pei,out + kei,out)

Nomenclature
fi = flowrate of component i,
hi = specific enthalpy,
pei = specific potential energy,
kei = specific kinetic energy
W = mechanical work done on system
Q = heat input to system
Specific quantities are amounts per mass or
per mole.

Equations continued
Changes in ke & pe smaller than enthalpy
(1)
i fi,out.hi,out i fi,in.hi,in = Q + W
NB. fi.hi = product of flowrate & specific
enthalpy = total rate of energy transport
with component i.
Impossible to measure absolute values of
enthalpy

Equations continued
Possible only to measure change in energy
corresponding to change of state
(T, P, concentration and phase).
let h = 0 for elements at 298K, 1atm
(standard state).
h(T) = hf,298 + hT + hphase + hP

h(T) = hf,298 + hT + hphase + hP

h(T) = specific enthalpy of molecules at
temp T and pressure P
hf,298 = heat of formation from elements at
298K, 1atm
hT = specific enthalpy change 298KT
hphase = latent heat of phase change
hP = specific enthalpy change 1atmP

Enthalpy Diagram (constant P)

Enthalpy Diagram (constant P)

Calculation of h
Need to calculate enthalpy changes for:
1 formation of the molecule from its
constituent elements
2 change of temperature at constant pressure
3 change of phase (not always required)
4 change of pressure at constant temperature
5 mixing of pure substances

1. Heats of Formation
Tabulated in reference books for 298K,
1atm (sometimes for two phases)
Calculate from bond energy contributions
normally evaluated at 298K, 1atm
represented by hf,i,298
often negative
eg C + 2H2 CH4 (g)
hf,CH4,298 = 74.88 kJ/mole

2. Change in Temperature at
Constant Pressure

hT = c p .dT
T2

T1

 

 

where cp (molar specific heat capacity at

constant pressure = dhdt
P
cp varies with temperature
correlated in reference books as function of
T for many substances.

2. Change in Temperature at
Constant Pressure
Often use average values over the
temperature range T1 to T2,
hT = cp.(T2 T1)
rate of enthalpy change, Q (in kW) given by
Q = fi.hT,i = fi.cp,i.(T2 T1)

3. Change of Phase
hphase 1 2 = 1 2
is a function of temperature
rate of enthalpy change, Q, given by
Q = fi.i

4. Change in Pressure at Constant

Temperature
Not discussed in detail here
hP = 0 for ideal gases
generally
h p = v.dP
P

1atm

at constant T
where v = molar volume

Calculation of hi(T)
Tables of data (eg Steam Tables)
Evaluate
hi(T) = hf,i,298 ( + hphase, I ) + hT, I
hi(T) = hf,i,298 ( + i,298 ) + cp,i.(T 298)
hi(T) is effectively the heat of formation of i at
temperature T from elements at 298K
hf,i = hf,i,298 ( + i,298 ) + cp,i.(T 298)
i,298 is calculated at 298K
only used if hf,i,298 is for other phase cp,i
refers to the correct phase at temperature T.

Enthalpy Diagram

Enthalpy Diagram

No reaction
fi,out = fi,in = fi
so
i fi,out.hi,out i fi,in.hi,in = Q + W
simplifies to
i fi.(hi,out hi,in) = Q + W
or
i fi. hi = Q + W

(1)

(2)

Example 1 Enthalpy Balance

around an Oil Blender
Mix 40kmol/h octane at 80oC with
60kmol/h of hexane at 20oC.
Evaluate specific molar enthalpy of octane
and hexane feeds and specific molar
enthalpy of octane and hexane in product.
Determine the mixture temperature, T.
Show that heats of formation are not
required in calculating T.

Data
Component

MJ/kmol

298 g
l

MJ/kmol

Cp(l)

Hexane

167.27

31.65

0.216

Octane

208.55

41.52

0.276

f,298(g)

MJ/kmolK

Chemical Reactions
fi,in only equals fi,out for species not involved
in reaction.
difference between standard heat of
formation of products and that of reactants
for 1 mole extent of reaction is standard
heat of reaction, hR,298.
hR,298 = i i. hf,i,298

Chemical Reactions cont

Formation of products from reactants
return of reactants to elements + formation
of products from elements
hR = reactants. h f,reactants
+ products. h f,products
Total heat absorbed in reaction, Q is
Q = . hR = . i i. hf,i

Heat of reaction
eg for
NH3(g) + CH4(g) 0.5N2 + C + 3.5H2 HCN(g) + 3 H2(g)

Is sum of
NH3(g) 0.5N2 + 1.5H2
CH4(g) C + 2 H2
0.5N2 + C + 0.5H2 HCN(g)
3 ( H2 H2(g))
(hf = 0)

hR = hf,HCN (g) + 3hf,H2(g) hf,NH3(g) hf,CH4(g)

hR = i i. hf,i
Q = . hR

Chemical Reactions cont

Returning to equation (1), and substituting for hi,out
and hi,in (hf,i,298 in correct phase).
i fi,out.hi,out i fi,in.hi,in = Q + W
i fi,out.(hf,i,298 + cp,i.(Tout 298)) fi,in.(hf,i,298 +
cp,i.(Tin 298)) = Q + W
But hf,i,Tout = hf,i,298 + cp,i.(Tout 298)
Thus i fi,out.(hf,i,298 + cp,i.(Tout 298)) = i fi,out.hf,i,Tout
and i fi,in.(hf,i,298 + cp,i.(Tin 298)) = i fi,in.(hf,i,Tout +
cp,i.(Tin Tout))

Chemical Reactions cont

Thus
i fi,out.hf,i,Tout i fi,in.(hf,i,Tout + cp,i.(Tin Tout)) = Q + W

or
i (fi,out fi,in).hf,i,Tout + i fi,in.cp,i.(Tout Tin) = Q + W

But,
fi,out = fi,in + .i
so
i .i.hf,i,Tout + i fi,in.cp,i.(Tout Tin) = Q + W
or . i i.hf,i,Tout + i fi,in.cp,i.(Tout Tin) = Q + W
so, substituting hR and rearranging
i fi,in.cp,i.(Tout Tin) + .hR = Q + W
(3)

Chemical Reactions cont

For multiple reactions, equivalent reasoning gives
i fi,in.cp,i.(Tout Tin) + k k.hR,k = Q + W
(4)
k extent of reaction k
hR,k heat of reaction k at temp Tout.

Procedure
1 Draw and label the process flowsheet
2 Determine flowrates and compositions from
a material balance.
3 Determine hR and for each reaction.
4 Using equation (3) or (4) and the specific
heats, solve to determine the unknown
(either T or Q in most cases).

Further Note on Chemical

Reactions
For most reactors, W = 0
isothermal reactor (Constant temp.)
.hR = Q
adiabatic reactor (no heat enters system),
Q = 0,
i fi,in.cp,i.(Tout Tin) + .hR = 0

Further Note on Chemical

Reactions cont
hR,k depends on precise reaction equation.
e.g. If for
A + BC
hR = y kJ/kmol,
then for
2A + 2B 2C
hR = 2y kJ/kmol
The rate of energy addition = .hR.

Example 2 Enthalpy Balance

around an Isothermal Reactor

Produce 81te/day HCN

Conversion methane 90%
ammonia provided in 5% excess
reactor operates isothermally at 1250C.
CH4 (g) + NH3 (g) HCN (g) + 3H2 (g)
hR = 251.2MJ/kmol
Determine rate of heat supply to reactor

Procedure
1 Draw and label the process flowsheet
2 Determine flowrates and compositions from
a material balance.
3 Determine hR and for each reaction.

Solution

Procedure
1 Draw and label the process flowsheet
2 Determine flowrates and compositions from
a material balance.
3 Determine hR and for each reaction.
4 Using equation (3) or (4) and the specific
heats, solve to determine the unknown
(either T or Q in most cases).

Solution
diagram drawn shows mass balance data.
hR endothermic at 251.2MJ/kmol
is 3000kmol/day
For an isothermal reactor .hR = Q
so
Q = .hR = 3000 251.2/(24 3600) = 8.72MW
This is the rate at which heat must be provided.

Example 3 Enthalpy balance

non-isothermal Reactor

Methane feed flowrate 64 te/day

Methane conversion 100%
ammonia in 10% excess
Oxygen as air (100% conversion)
5% ammonia feed forms N2 and H2O
40% of heat released radiated away
Gauze temp to remain at 1370K
Determine reactant feed temperature

Procedure
1 Draw and label the process flowsheet
2 Determine flowrates and compositions from
a material balance.

Solution

Procedure
1 Draw and label the process flowsheet
2 Determine flowrates and compositions from
a material balance.
3 Determine hR and for each reaction.

Solution
diagram drawn shows mass balance data.
Reaction (1)

hR,1 = 606.2MJ/kmol,

1 = 4000kmol/day.

Reaction (2)

hR,2 = 409MJ/kmol,

2 = 220kmol/day.

Procedure
1 Draw and label the process flowsheet
2 Determine flowrates and compositions from
a material balance.
3 Determine hR and for each reaction.
4 Using equation (3) or (4) and the specific
heats, solve to determine the unknown
(either T or Q in most cases).

Specific Heat data

Component
H2
N2
O2
H 2O
NH3
CH4
HCN

Cp,i (kJ/kmol.K)
30
30
30
45
60
75
45

Solution
Total heat of reaction

(4000 606.2) + (220 409) = 2515000MJ/day.

Heat radiated away (Q) is 40% of this,

(or Q = 1006000MJ/day).
i fi,in.cp,i.(Tout Tin) + k k.hR,k = Q + W
{(400075) + (440060) + (616530) + (2319030)} (1370Tin)
2515000000 = 1006000000 + 0

Therefore
Tin = 1370 1509000000/1444650 = 325K
The reactants inlet temperature is 325K or 52C.