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

hT = c p .dT
T2 T1

2. Change in Temperature at Constant Pressure

where cp (molar specific heat capacity at constant pressure = dh dt 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

f,298(g)

MJ/kmol

298 gl

Cp(l)

MJ/kmolK

Hexane Octane

167.27 208.55

31.65 41.52

0.216 0.276

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 = i i. hf,i Q = . hR

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

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.