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Paul Ashall, 2008

Paul Ashall, 2008

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

Paul Ashall, 2008

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
**

Paul Ashall, 2008

Energy balance W mass in mass out system Hin Q Hout Paul Ashall. 2008 .

2008 .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 Paul Ashall.

Steady state/non-steady state Non steady state accumulation/depletion of energy in system Paul Ashall. 2008 .

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 &Paul development Ashall. 2008 etc .

W terms = 0 Q = H2 – H1 or Q = ΔH .e. 2008 .e.. the enthalpy (heat) transferred to or from the system Paul Ashall.. Q is the difference in total enthalpy i. k. where H2 is the total enthalpy of output streams and H1is the total enthalpy of input streams.e.Enthalpy balance p.

heat supplied to system. 2008 . heat removed from system Q +ve (H2>H1).continued Q –ve (H1>H2). Paul Ashall.

65 deg cent. H = 2793..Example – steam boiler Two input streams: stream 1.120 kg/min.4 kJ/kg Paul Ashall. H = 125.). 30 deg cent..7 kJ/kg. water. saturated steam(17 atm. stream 2 – 175 kg/min. 204 deg cent. 2008 . H= 272 kJ/kg One output stream: 295 kg/min.

large temperature changes etc Q = ΔH (enthalpy balance) Basis for calculation 1 min. Steady state Q = Hout – Hin Q = [295 x 2793. terms relative to enthalpy changes for processes involving phase changes.e.4] – [(120 x 125. 2008 . chemical reactions.continued Ignore k. and p.67 x 105 kJ/min Paul Ashall.e.7) + (175 x 272)] Q = + 7.

Steam tables Enthalpy values (H kJ/kg) at various P. 2008 . T Paul Ashall.

2008 .Enthalpy changes Change of T at constant P Change of P at constant T Change of phase Solution Mixing Chemical reaction crystallisation Paul Ashall.

2008 .Latent heats (phase changes) Vapourisation (L to V) Melting (S to L) Sublimation (S to V) Paul Ashall.

Mechanical energy balance 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. 2008 . Δh = h2 –h1 Bernoulli equation (F=0. W=0) Paul Ashall. Δ v2 = v22 –v12.

2008 .Bernoulli eqtn. Paul Ashall. Water flows between two points 1. The pipe internal diameters are 0. Point 2 is 50 m higher than point 1..Example .5 cm at point 1 and 1 cm at point 2. The pressure at point 2 is 1 atm. Calculate the pressure at point 2.2. The volumetric flow rate is 20 litres/min.

continued ΔP/ρ + Δv2/2 + gΔh +F = W ΔP = P2 – P1 (Pa) Δ v 2 = v 22 – v 12 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 Paul Ashall. 2008 .

000333 m3/s v1 = 0.6 bar) Paul Ashall.60) m3/s = 0.81.50 = 0 P1 = 456825 Pa (4.24 m/s (101325 .97)2]/2 + 9.97 m/s v2 = 0.24)2 – (16.continued Volumetric flow is 20/(1000.000333/ (π(0. 2008 .P1)/1000 + [(4.005)2) = 4.000333/(π(0.0025)2) = 16.

Heat capacities/specific heats (solids. liquids.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 Paul Ashall. 2008 . gases.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.

T1 ΔH = [aT + bT2 + cT3 + dT4] 2 3 4 Calculate values for T = T2.check units for Cp! Paul Ashall. d are coefficients ΔH = integralCpdT between limits T2.where a. Cp = a + bT + cT2 + dT3 .continued e. c. b. 2008 .g. T1 and subtract Note: T may be in deg cent or K .

87 x 10-9 T3. 2008 . cent..572 x 10-5T2 – 2.22 x 10-2T + 0. through a gas heater from 20 to 100 deg. (use mean Cp value 29.1J mol-1 K-1 or Cp = 29 + 0. where T is in deg cent) Paul Ashall.Example Calculate the enthalpy required to heat a stream of nitrogen gas flowing at 100 mole/min.

Reid et al. ch. Chem. 8. R. Gold & G. 2008 . 4th edition. 1987 Estimating thermochemical properties of liquids part 7. McGraw Hill. pp321-324 ‘PhysProps’ Paul Ashall. 1969.Ogle.Heat capacity/specific heat data Felder & Rousseau pp372/373 and Table B10 Perry’s Chemical Engineers Handbook The properties of gases and liquids. Eng.heat capacity. 6.. Vol.. 3rd edition. Eng. P. p130 Coulson & Richardson Chem.

[Need Cp (benzene. Cp (toluene. vapour).] Paul Ashall. 2008 . latent heat of vapourisation benzene.Example – change of phase A feed stream to a distillation unit contains an equimolar mixture of benzene and toluene at 10 deg cent. vapour).The vapour stream from the top of the column contains 68. latent heat of vapourisation toluene. liquid). and the liquid stream from the bottom of the column contains 40 mol% benzene at 50 deg cent.4 mol % benzene at 50 deg cent. Cp (benzene. Cp (toluene. liquid).

ΔHofC. (kJ/mol) aA + bB cC + dD -a -b +c +d (stoichiometric coefficients. 2008 .a ΔHofA .bΔHofB Paul Ashall.Energy balances on systems involving chemical reaction Standard heat of formation (ΔHof) – heat of reaction when product is formed from its elements in their standard states at 298 K. νi) ΔHofA. ΔHofD (heats of formation) ΔHoR = c ΔHofC + d ΔHofD . 1 atm. ΔHofB.

Heat (enthalpy) of reaction ΔHoR –ve (exothermic reaction) ΔHoR +ve (endothermic reaction) Paul Ashall. 2008 .

where ζ is extent of reaction and is equal to [moles component. 2008 . out – moles component i.Enthalpy balance equation reactor Qp = Hproducts – Hreactants + Qr Qp – heat transferred to or from process Qr – reaction heat (ζ ΔHoR).i. in]/ νi Paul Ashall.

2008 temperature of 25 deg cent .Hreactants Hproducts system Qr +ve Qp -ve Note: enthalpy values must be calculated with reference to a Paul Ashall.

Consider any additional enthalpy changes Solve enthalpy balance equation Paul Ashall. 2008 .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).

Energy balance techniques Adiabatic temperature: Qp = 0 Paul Ashall. 2008 .

Examples Reactor Crystalliser Drier Distillation Paul Ashall. 2008 .

R. R.Rousseau Paul Ashall. Reid Elementary Principles of Chemical Processes.References The Properties of Gases and Liquids.Felder and R.M.W. 2008 .

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