Fall 2015-2016

 Concerned with energy changes and energy flow in a

chemical process.
 Conservation of energy – first law of thermodynamics i.e.
accumulation = energy input – energy output

ChE 495 2
 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

ChE 495 3
 W

mass in mass out

system
Hin Hout

ChE 495 4
 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

*International Union of Pure and Applied Chemistry

ChE 495 5
 Non steady state - accumulation/depletion of energy in
system

ChE 495 6
 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
ChE 495 7
 If P.E., K.E., W terms = 0
 Q = H2 – H1 or Q = ΔH

, 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

ChE 495 8
 Q –ve (H1>H2), heat removed from system
 Q +ve (H2>H1), heat supplied to system.

ChE 495 9
Two input streams:
Stream # 1: 120 kg/min. water, 30 oC, H = 125.7 kJ/kg;
Stream # 2: 175 kg/min, 65 oC, H= 272 kJ/kg

One output stream: 295 kg/min. saturated steam(17 atm,

204 oC), H = 2793.4 kJ/kg

ChE 495 10
Ignore K.E. and P.E. terms relative to enthalpy changes
for processes involving phase changes, chemical
reactions, large temperature changes etc

Q = ΔH (enthalpy balance)
Basis for calculation 1 min.
Steady state
Q = Hout – Hin
Q = [295 x 2793.4] – [(120 x 125.7) + (175 x 272)]
Q = + 7.67 x 105 kJ/min  Heat Added

ChE 495 11
 Enthalpy values (H kJ/kg) at various P, T

ChE 495 12
 Change of T at constant P
 Change of P at constant T
 Change of phase
 Solution
 Mixing
 Chemical reaction
 Crystallisation

ChE 495 13
 Vaporisation (L to V)
 Melting (S to L)
 Sublimation (S to V)

ChE 495 14
 Consider mechanical energy terms only
 Application to flow of liquids
ΔP + Δ v2 + g Δh +F = W
ρ 2
where W is work done on system by a pump and F is
frictional energy loss in system (J/kg)
ΔP = P2 – P1; Δ v2 = v22 –v12; Δh = h2 –h1

 Bernoulli equation (F=0, W=0)

ChE 495 15
Water flows between two points 1,2. The volumetric flow
rate is 20 litres/min. Point 2 is 50 m higher than point
1. The pipe internal diameters are 0.5 cm at point 1 and
1 cm at point 2. The pressure at point 2 is 1 atm..
Calculate the pressure at point 2.

ChE 495 16
ΔP/ρ + Δv2/2 + gΔh +F = W

ΔP = P2 – P1 (Pa)
Δv2 = v22 – v12
Δh = h2 - h1 (m)
F= frictional energy loss (mechanical energy loss to
system) (J/kg)
W = work done on system by pump (J/kg)
ρ = 1000 kg/m3

ChE 495 17
Volumetric flow is 20/(1000.60) m3/s
= 0.000333 m3/s
v1 = 0.000333/(π(0.0025)2) = 16.97 m/s
v2 = 0.000333/ (π(0.005)2) = 4.24 m/s

(101325 - P1)/1000 + [(4.24)2 – (16.97)2]/2 + 9.81.50 = 0

P1 = 456825 Pa (4.6 bar)

ChE 495 18
 ‘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
ΔH = 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

ChE 495 19
e.g. Cp = a + bT + cT2 + dT3
,where a, b, c, d are coefficients

ΔH = integralCpdT between limits T2, T1

ΔH = 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!

ChE 495 20
Calculate the enthalpy required to heat a stream of
nitrogen gas flowing at 100 mole/min., through a gas
heater from 20 to 100 deg. cent.
(use mean Cp value 29.1J mol-1 K-1 or Cp = 29 + 0.22 x 10-
2T + 0.572 x 10-5T2 – 2.87 x 10-9 T3, where T is in deg

cent)

ChE 495 21
 Felder & Rousseau pp372/373 and Table B10
 Perry’s 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’

ChE 495 22
A feed stream to a distillation unit contains an equimolar
mixture of benzene and toluene at 10 deg cent.The vapour
stream from the top of the column contains 68.4 mol %
benzene at 50 deg cent. and the liquid stream from the
bottom of the column contains 40 mol% benzene at 50 deg
cent.

[Need Cp (benzene, liquid), Cp (toluene, liquid), Cp

(benzene, vapour), Cp (toluene, vapour), latent heat of
vapourisation benzene, latent heat of vapourisation
toluene.]

ChE 495 23
 Standard heat of formation (ΔHof ) – 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, νi)
ΔHofA, ΔHofB, ΔHofC, ΔHofD (heats of formation)

ΔHoR = c ΔHofC + d ΔHofD - a ΔHofA - bΔHofB

ChE 495 24
 ΔHoR –ve (exothermic reaction)
 ΔHoR +ve (endothermic reaction)

ChE 495 25
 Qp = Hproducts – Hreactants + Qr

Qp – heat transferred to or from process

Qr – reaction heat (ζ ΔHoR), where ζ is extent of reaction

and is equal to:
ζ=[moles component,i, out – moles component i, in]/ νi

ChE 495 26
 Hproducts
Hreactants
System
Qr

+ve
Qp

-ve

Note: enthalpy values must be calculated with reference to a

temperature reference
ChE 495 27
 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

ChE 495 28
 Adiabatic temperature: Qp = 0

ChE 495 29
 The Properties of Gases and Liquids, R. Reid
 Elementary Principles of Chemical Processes,
R.M.Felder and R.W.Rousseau

ChE 495 30