THERMODYNAMICS AND HEAT CAPACITIES

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Thermodynamics & Heat Capacities

LEARNING OBJECTIVES

At the end of the day the trainee shall be able to : - Perform simple heat balances

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Thermodynamics & Heat Capacities

THE JOULES EXPERIMENT

W

W: work done on the water DT: change in water temperature Joule found that a definite amount of work was required per unit mass of water for every degree of temperature rise caused by the stirring and there was a quantitative relationship between work and heat and, therefore, that heat is a form of energy.
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T W Heat is a form of energy

Thermodynamics & Heat Capacities

THE FIRST LAW OF THERMODYNAMICS

For a closed (constant-mass)

system: DE = Q W
DE : Total energy change of the system Q : Heat added to the system W : Work done by the system W

The total energy change of a

closed system is equal to the heat transferred to the system minus the work done by the system.
Q

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Thermodynamics & Heat Capacities

THE FIRST LAW OF THERMODYNAMICS

The first law of thermodynamics may be stated in many other ways One of these is as follows : Although energy assumes many forms, the total quantity of energy is constant, and when energy disappears in one form it appears simultaneously in other forms. The first law of thermodynamics is a generalization of the law of the conservation of energy. This is a law to be obeyed by every process engineers.
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Thermodynamics & Heat Capacities

INTERNAL ENERGY

Internal Energy (U) :

Energy of the molecules making up the substance E = U + Ek + Ep U = E - Ek + Ep E = total energy U = Internal Energy Ek = kinetic energy Ep = potential energy

If no change in kinetic and potential energy:

E = U = Q - W
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Thermodynamics & Heat Capacities

ENTHALPY

The sum of the internal energy and the product

of pressure and volume appears frequently. That combination is called enthalpy : H = U + pV H = U + pV

Steam tables and other property tables usually

give energy as enthalpy

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Thermodynamics & Heat Capacities

ENTHALPY
Based on the standard state at a given temperature Can be added : H(0,100) = H(0,50)+H(50,100) = H(0,200)-H(200,100) H = Q = m C P dT

H = m C P dT + m
0

50

100

50

C P dT = m

100

0
100

C P dT

H = m

200

CP dT m

200

100

C P dT = m CP dT
0
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Thermodynamics & Heat Capacities

HEAT CAPACITY

h = m cp t [kJ]

m = throughput - [kg or Nm] cp = specific heat - [kJ/kg x T or kJ/Nm x T K K] at constant pressure t = difference of temperature between the measured temperature and the reference of the heat balance (in C)
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Thermodynamics & Heat Capacities

HEAT CAPACITY
Heat capacity: the quantity of heat required to raise the temperature of a given mass (or mole) of a material by 1 degree.
C= 1 dQ n dT

Q =

nC

dT

Heat Capacity of Oxygen

0.27 0.26 0.25 0.24 0.23 0.22 0.21 0 200 400 600 800 Te mpe rature ( C)

More practically, the heat required to change the temperature fromT1 to T2 is the area under the curve (the integral) between those two temperatures.
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Cp (kcal/kg. K)

Thermodynamics & Heat Capacities

HEAT CAPACITY VS SPECIFIC HEAT

Heat capacity is on mole basis (kcal/kgmole. C) Some people will use C for heat capacity
Q =

nC 'dT

Specific heat is the heat capacity per unit mass (kcal/kg. C) C will be used for specific heat
Q =

m C dT
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Could be confusing. Always make sure of the units

Thermodynamics & Heat Capacities

Cp vs Cv
CV : heat capacity at constant volume
U = Q = m CV dT

CP : heat capacity at constant pressure

H = Q = m C P dT

For an ideal gas :

C ' P C 'V = R

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Thermodynamics & Heat Capacities

HEAT CAPACITY OF A MIXTURE

cp mixture = xAcpA + xBcpB + xCcpC

where xA, xB, xC : mass fractions of component A, B, C

cpA, cpB, cpC : specific heat (mass) of A, B, C

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Thermodynamics & Heat Capacities

REFERENCE TEMPERATURE

For heat calculation, any reference

temperature is valid as long as consistent and specified.

Recommended : (Convenient)
0 = 273.15 = 32 = 491.67 C K F R

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Thermodynamics & Heat Capacities

HEAT CAPACITY CORRELATIONS

Lafarge standard form:

c p = a + bT + cT + d
with T : temperature in K

1 T

in kcal/kg. K

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Thermodynamics & Heat Capacities

Cpmean

CP(T) gives the rate of heat content at a given temperature. Absolute temperature is required (K)
T1

H = Q =

T1

C P dT =

a + bT + cT
T1 T0

T0

T0

d dT T2

b c d = aT + T 2 + T 3 2 3 T

1 b c 1 = a (T1 T0 ) + T12 T02 + T13 T03 d 2 3 T1 T0

a (T1 T0 ) + C P m ean =

1 b c 1 T12 T02 + T13 T03 d 2 3 T1 T0 T1 T0

H = Q = C Pmean ( T1 , T0 ) ( T1 T0 )
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Thermodynamics & Heat Capacities

Cpmean - Example
Calculate CPmean of nitrogen at 1000 using the Lafarge standard C correlation and the constants given below. Equation constants :
Tlimit a b c 2.76050E-8 -1.05755E-8 d 6.53840E+2 -7.11335E+3 298 to 800 K 2.32210E-1 2.14938E-5 800 to 2200K 2.42450E-1 5.44079E-5 1000 = 1273K C

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Thermodynamics & Heat Capacities

Cpmean Example (Contd.)

First Integration From 0 to 527 (273 to 800 : C C K K) Q1 = [(2.32210E-1)*(800-273)] + [((2.14938E-5)/2)*(800^2-273^2)] + [((2.76050E-8)/3)*(800^3-273^3)] [(6.53840E+2)*(1/800-1/273)] = 122.375 + 6.077 + 4.524 + 1.578 = 134.553 kcal/kg
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Thermodynamics & Heat Capacities

Cpmean Example (Contd.)

Second Integration From 527 to 1000 (800 to 1273 : C C K K) Q2 = [(2.42450E-1)*(1273-800)] + [((5.44079E-5)/2)*(1273^2-800^2)] + [((-1.05755E-8)/2)*(1273^3-800^3)] [(-7.11335E+3)*(1/1273-1/800)] = 114.679 + 26.674 - 5.467 - 3.304 = 132.582 kcal/kg
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Thermodynamics & Heat Capacities

Cpmean Example (Contd.)

Cpmean : = (Q1 + Q2) / (T1 - T0) = (134.554 + 132.582) / (1273 - 273) = 0.2671 kcal/kg. K

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Thermodynamics & Heat Capacities

THERMODYNAMIC ADD IN Cpmean, Cpgas and Cpmat

Return Cpmean in kcal/kg.C Standard within Lafarge group For all typical gases in cement industry: O2, N2, H2, SO2, CO, A, Air, Water vapor For most materials in cement industry: SiO2, Al2O3, Fe2O3, CaCO3, CaO, MgCO3, MgO, CaSO4 Coal, Steel, Raw mix, clinker Usage: =Cpgas("CO2",N17)*N17 where :N17 cell contains temperature in C
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Thermodynamics & Heat Capacities

THERMODYNAMIC ADD IN ENTHALPY

Calculates the enthalpy of a material at a given temperature Equivalent to
H = Cpmean(T) x T

Returns H in kcal/kg Usage: = Enthalpy("CO2",N17) where : N17 cell contains temperature in C

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Thermodynamics & Heat Capacities

THERMODYNAMIC ADD IN TEMPERATURE

Returns temperature from enthalpy in C Usage: = Temperature("CO2",N17) where : N17 cell contains enthalpy in kcal/kg

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Thermodynamics & Heat Capacities

THERMODYNAMIC ADD IN Cpmean, Cpgas and Cpmat

Enthalpy change between two temperatures T1 and T2:

T2

H = Q = CP dT = CP dT CPdT
T1 T0 T0
T0

T2

T1

CP

Q1
T1

Q2
T2

= Cpgas("CO2",T2)*T2 - Cpgas("CO2",T1)*T1 or = Enthalpy("CO2",T2) - Enthalpy("CO2",T1)

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Thermodynamics & Heat Capacities

PHASE CHANGE
Watson correlation:

H2 Tc T2 = H1 Tc T1
Tc : critical temperature

0.38

Critical temperature of water : 374.2 C

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Thermodynamics & Heat Capacities

PHASE CHANGE - Example

What is the heat of vaporization of water at 50C knowing that it is 538.7 kcal/kg at 100C?
Tc = 374.2C
0.38

374.2 50 H2 = 538.7 374.2 100

= 574.1 kcal / kg

At which temperature is the heat of vaporization 0.0 kcal/kg?

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Thermodynamics & Heat Capacities

ENTHALPY OF WATER VAPOR

The standard state of water at reference temperature

(0 is liquid. C) Water vapor contains sensible heat (heat to raise vapor from 0 to the specified temperature) and latent heat C (heat to evaporate the liquid). Many paths are equivalent Heat (kcal/kg) Heat (kcal/kg)
vapor

vapor evaporation
liquid

evaporation
liquid

100 Temperature ( C)

200

100 Temperature ( C)

200

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Thermodynamics & Heat Capacities

Exercise 3.1 WATER VAPOR Question :

What is the heat content of water vapor at 200 using 0 as the reference C C temperature?

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Thermodynamics & Heat Capacities

Exercise 3.1 WATER VAPOR Solution :

Heat (kcal/kg)
vapor

evaporation
liquid

100 Temperature ( C)

200

Path-1: Evaporation at 100 C heat to raise liquid water from 0 to 100 : C C 100.31 kcal/kg heat to evaporate water 100 : C 538.70 kcal/kg heat to raise vapor water from 100 to 200 : 45.69 kcal/kg C C 684.70 kcal/kg
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Thermodynamics & Heat Capacities

Exercise 3.1 WATER VAPOR Solution : (contd.)

Heat (kcal/kg) vapor evaporation
liquid

100 Temperature ( C)

200

Path-2 : Evaporation at 200 C heat to raise liquid water from 0 to 200 : C C heat to evaporate water 200 : C

202.75 kcal/kg 453.40 kcal/kg 656.15 kcal/kg

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Thermodynamics & Heat Capacities

Exercise 3.1 WATER VAPOR Solution : (contd.)

Path-1: Evaporation at 100 C Path-2 : Evaporation at 200 C 684.70 kcal/kg 656.15 kcal/kg

Difference : 4.2% => The method according to first path was found accurate against Steam Tables

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Thermodynamics & Heat Capacities

HEAT BALANCES

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Thermodynamics & Heat Capacities

HEAT BALANCE Energy cannot be created or destroyed but may be converted from one form to another Energy in = Energy out MASS BALANCE

massin = massout
HEAT BALANCE

heatin = heatout
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Thermodynamics & Heat Capacities

HEAT BALANCE
3 - Point Junction : Balance around three points
1 OR 2 3

Mass Balance m1 + m2 = m3

Heat Balance m 1h 1+ m 2h 2 = m 3h 3

Component Balance m1c1+ m2c2= m3c3

In order to solve a 3 junction problem it is sufficient to know only e.g. mass flow, but knowing one property of all 3 flows (e.g. heat, O2 content, Blaine)
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Thermodynamics & Heat Capacities

Exercise 4.1 : 3 - POINT JUNCTION Question :

In Fredonia, the air for the coal mill is taken from the kiln hood.
To prevent excessive temperature to the mill, some cold air is mixed with that hot air with a bleed-in damper. The only location where the air flow could be measured is after that bleed-in damper. temperature was 110 The air from the kiln hood was at 450 C. C and the ambient air 25 Calculate the air flow from the kiln hood. C.
kiln hood 450 C coal mill 110 C

On one occasion, the combined flow was 12611 Nm/h and its

cp=1,0339 kJ/kg.K
ambiant air 25 C

cp=1,0071 kJ/kg.K

cp=1,0057 kJ/kg.K
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Thermodynamics & Heat Capacities

Exercise 4.1 : 3 - POINT JUNCTION Solution :

Kiln Hood Temperature ( C) Cp (kJ/kg K) V (Nm3/h) m (kg/h) h (kJ/h) 450 1.0339 2454 3171 1475467 Ambient Air 25 1.0057 10157 13127 330037 Coal Mill 110 1.0071 12611 16298 1805503 0 0
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Balance Check

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Thermodynamics & Heat Capacities

Exercise 4.2 : HEAT BALANCE Question :

Malogozscz plant in Poland is planning to build a Cl-Bypass, where part
of the kiln inlet gas is extracted, cooled by fresh air in a mixing chamber and de-dusted in a bag filter. In parallel the plant is executing a second project which covers the complete re-design of the gas conditioning tower (hereinafter called GCT) plus a new kiln filter. The clean bypass gas is mixed with the preheater exit gas after ID fan before GCT. The mixed gases are conditioned in the GCT and de-dusted in the kiln filter before going to the stack.

The bypass system is well sized, but the kiln filter and GCT need to be
mathematically checked, if the proposed water amount for injection is sufficient (11 [m/h]) for the proposed bag quality (P84: continuous operation temperature 220 [C]) and the proposed filtration area (6400 [m]) is sufficient for an air to cloth ratio of 1 [m/(min m)].
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Thermodynamics & Heat Capacities

Exercise 4.2 : HEAT BALANCE

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