THERMODYNAMICS

Course no: CHE C311 / F213 Dr. Srinivas Krishnaswamy

1st Semester 2011 2013 DEPT. OF CHEMICAL ENGG. BITS PILANI, K. K. BIRLA GOA CAMPUS

Contents of lectures 15, 16 and 17

The concept of specific heat Specific heat at constant volume Specific heat at constant pressure Internal energy, enthalpy and specific heat relations for ideal gases Pressure enthalpy diagram Calculation of internal energy and enthalpy of a pure substance Application of first law to non-flow processes

The concept of specific heat

We know that it takes different amounts of energy to raise the temperature of identical masses of different substances by 1 degree For example 4.5 kJ are needed to raise the temperature of 1 kg of iron from 20 to 30 oC whereas it takes 9 times this energy (41.8 kJ to be exact) to raise the temperature of 1 kg of water by the same amount Why is this so? This needs to be understood

The concept of specific heat

This is because different substances have different energy storing capabilities It is thus desirable to have a tool that enables us to compare the energy storage capabilities of various substances. Such a tool is specific heat It is defined as the energy required to raise the temperature of a unit mass of a substance by one degree In general however this energy would depend on how the process is executed

The concept of specific heat

The SI unit of specific heat is kJ/kg.K Since heat transfer is a path function, specific heat is a path function Denoting specific heat by c, we have by definition c = q / T

Specific heat at constant volume and pressure

It is viewed as the energy required to raise the temperature of a unit mass of a substance by one degree as the volume is maintained constant (cv) The energy required to do the same at constant pressure is the specific heat at constant pressure (cP) The specific heat at constant pressure will always be greater than that at constant volume because at constant pressure the system can change volume and energy for this expansion must be supplied

Specific heat at constant volume From definition of specific heat cv = (q / T )v = (1/m)(Q/ T )v Since P d = 0, Q = U (from First Law) cv = (u / T )v = (1/m)(U/ T )v This is nothing but the change in internal energy with temperature

Specific heat at constant pressure From definition of specific heat cP = (q / T )P = (1/m)(Q/ T )P Since Q = H (for constant pressure reversible process) cP = (h / T )P = (1/m)(H/ T )P This is nothing but the change in enthalpy with temperature

Specific heat at constant volume and pressure

Unlike c, cP and cv are state functions and hence are properties The expressions for both contain thermodynamic properties and can be written as cP = f (h, T, P ) and cv = f (u, T, ) The difference between cP and cv is not very large

Specific heat at constant volume and pressure

Note the equations for cP and cv are property relations and as such independent of the type of process Both cP and cv are temperature dependent For a mass of 1kg, specific heat values will be different if temperature changes from 300 301 K as compared to a change of temperature from 1000 1001 K For solids and liquids specific volume is small and its changes insignificant. There is only one specific heat. Thus Q = dh = du = cdT

Internal energy, enthalpy and specific heat relations for ideal gases
For an ideal gas, it is known that P = RT Joule conducted experiments and showed that internal energy is a function of temperature only and not of pressure or specific volume, i,.e. u = f (T ). Not true however for gases that deviate from ideal gas behavior From definition of enthalpy we have h = u + P = u + RT

Internal energy, enthalpy and specific heat relations for ideal gases
Since R is a constant and u = f (T ), it

follows that h = f (T ) Since u and h = f (T ) for an ideal gas,

cP and cv will depend utmost on temperature only At a fixed temperature, for an ideal gas u, h, cP and cv have fixed values whatever the pressure or specific volume

Internal energy, enthalpy and specific heat relations for ideal gases
Thus for ideal gases du = cv (T ) dT and dh = cP (T ) dT The change in internal energy or enthalpy for an ideal gas during a process from state 1 to 2 u = u2 u1 = cv ( T ) dT h = h2 h1 = cP ( T ) dT To carry out these integrations relations for cP and cv as functions of T are required

Internal energy, enthalpy and specific heat relations for ideal gases
At low pressures all real gases approach ideal gas behavior and their specific heats are called ideal gas or zero pressure specific heats and denoted as cPo and cvo The dependence of ideal gas specific heat on temperature are available for most gases and expressed in polynomial form Thus use of ideal gas specific heat data though limited to low pressures can be extended to moderately high pressures with reasonable accuracy as long as deviation from ideal gas behavior is small

Internal energy, enthalpy and specific heat relations for ideal gases
While finding specific heat using integration is simple, it is laborious A better method would be to use u and h values for ideal gases have been tabulated The tables values are not absolute, but obtained using a arbitrary reference point (zero Kelvin state) at which enthalpy and internal energy are assigned zero values The choice of the reference point has no effect on the u or h calculations

Internal energy, enthalpy and specific heat relations for ideal gases
Specific heat of complex molecules (with more than 2 atoms) are always higher than the specific heat of molecules with one atom and increase with temperature The variation of specific heat with temperature for small temperature intervals may however be approximated as linear. For monatomic gases it is constant over the entire range u2 u1 = cv,av (T2 T1) and h2 h1 = cp,av (T2 T1)

Internal energy, enthalpy and specific heat relations for ideal gases
u or h are not restricted to any kind of process The presence of constant volume specific heat in an equation should not lead one to believe that the equation is valid for a constant volume process only On the contrary u = cv (T2 T1) is applicable to any process A similar argument can be presented for cP and h

Internal energy, enthalpy and specific heat relations for ideal gases
1.

2.
3.

There are thus 3 ways to determine internal energy or enthalpy changes for an ideal gas: By using tabulated u or h data By using specific heat relations and a function of temperature and integrating By using average specific heats especially when property tables are not available. This result is reasonably accurate if the temperature interval is not very large

Specific heat relations for ideal gases

It has been noted that h = u + P = u + RT for an ideal gas Differentiating dh = du + RdT Replacing dh and du by cPdT and cvdT and dividing by dT cP = cv + R ---------- (kJ/kg.K) When the specific heats are given on a molar basis, R must be replaced by the Universal gas constant R

Specific heat relations for ideal gases

The ratio of two specific heats of a gas is called the specific heat ratio and denoted by k or where
k = = cP / cv This ratio also is a function of temperature, but the variation is mild This is also an ideal gas property

Problem
1 kg of air is heated at low pressure from 300 K to 500 K. Find the change in enthalpy: 1. Using the expression for zero-pressure specific heat for air 2. Using average value of specific heat of air of 1.017 kJ / kg.K Given cPo = 27.43 + 6.18 10-3 T 0.8987 10-6 T 2 kJ/kmol.K

Solution
Assuming air as an ideal gas (low pressure) h = cPo ( T ) dT = 5952 kJ / kmol Note that h is asked Since 1 kmol has a mass of 28.966 kg we get h = h / 28.966 = 205.5 kJ/kg Taking the average specific heat of air h2 h1 = cp,av (T2 T1) = 203.4 kJ /kg

Application of first law to non-flow processes

The first Law again:

Q W = U

REVERSIBLE CONSTANT VOLUME PROCESS For such a process PdV = 0, The heat transfer to the system is exactly equal in magnitude to the change in internal energy Qv = U

Application of first law to non-flow processes

REVERSIBLE CONSTANT PRESSURE PROCESS
Q = dH = dU + P dV CONSTANT TEMPERATURE ISOTHERMAL PROCESS This is essentially a quasi-equilibrium process since it can be achieved by performing it slowly. For an ideal gas, U = 0 so that

QT = W

Application of first law to non-flow processes

Thus in an isothermal compression or expansion of an ideal gas, heat transfer equal to the work done. In the case of real gases some of the heat goes to increase the internal energy of the gas ADIABATIC PROCESS

Q = 0 and hence Wad = - dU

Application of first law to non-flow processes

Thus when a closed system undergoes an adiabatic change of state, the work done is the same for all possible paths between the given initial and final state and is equal to the change in internal energy. In this matter it is immaterial if the process is reversible or irreversible In a reversible adiabatic process however since W = PdV from which it can be concluded that dU = -P dV and dH = VdP

Application of first law to non-flow processes

REVERSIBLE ADIABATIC PROCESS FOR AN IDEAL GAS For the reversible adiabatic case we have

du = -P d and dh = dP For an ideal gas, du = cvodT and dh = cPodT Therefore cvodT = -P d and cPodT = dP

Application of first law to non-flow processes

Dividing ( dP / P ) + (cPo / cvo) (d / ) = 0 Replacing (cPo / cvo) by k and integrating P k = C k is the adiabatic exponent. This equation applies only to reversible adiabatic process for an ideal gas for which T2 / T1 = (P2 / P1)(k 1 / k) = (1 / 2)(k 1)

Application of first law to non-flow processes

Consider a reversible adiabatic process for an ideal gas, i.e. Pk = C

The slope of this curve is dP / d = - k (P / ) Consider reversible isothermal process for an ideal gas, i.e. P = C The slope of this curve is dP / d = - (P / )

Application of first law to non-flow processes

It is evident that the slope of a reversible adiabatic process is steeper than that of a reversible isothermal line since k = 1 FREE EXPANSION PROCESS This is an irreversible adiabatic process in which no work is done. Since both Q and W = 0, U2 = U1 Free expansion is thus a constant internal energy process

Application of first law to non-flow processes

POLYTROPIC PROCESS The pressure volume relationship applicable to a reversible adiabatic process for an ideal gas can be extended by replacing the index k by n to a process in which heat transfer does take place. Such a process is polytropic and represented by the relation P n = C

Application of first law to non-flow processes

The polytropic law can be applied to all processes in general with or without heat transfer (reversible or irreversible) Index n can have any value from - to When n = 0, it is a constant pressure process When n = k, it is reversible adiabatic process for an ideal gas When n = 1, it becomes an hyperbolic process which for an ideal gas is an isothermal process

Application of first law to non-flow processes

Differentiation gives dP / d = - n (P / ) The slope for the process increases in the negative direction with increasing n The integrated form of the first law when n is not equal to 1 is Q = U2 U1 + [(P2V2 - P1V1) / (1 n)]

Application of first law to non-flow processes

In a polytropic process, there is some cooling during compression and heating during expansion The amount of heat transfer stands somewhere between no heat transfer of reversible adiabatic process and transfer process of all work done as heat (for an ideal gas) of the reversible isothermal process Depending on the magnitude of heat transfer, the value of n lies between 1 and k Reversible polytropic process lies between reversible adiabatic and reversible isothermal process

Application of first law to non-flow processes

Problem
One kg mass of air expands reversibly from 6.5 bar and 0.0135 m3 to a final volume of 0.1 m3. Find the final pressure, final temperature, work done, change in internal energy and heat interaction if the expansion is: a. Adiabatic b. Polytropic with n = 1.3 c. Isothermal

Solution
Adiabatic process, so q = 0 P11k = P22k gives the final pressure = 0.394 bar Initial and final temperatures can be found from P11 = RT1 and P22 = RT2 = 305.7 and 137.3 K respectively (k = 1.4) Work done = w = R (T2 - T1) / (1 n) = 120.8 kJ Internal energy change = u = cvo (T2 T1) = -120.8 kJ

Solution
For polytropic expansion final temperature and pressure can be found using similar formulae with n = 1.3 (0.481 bar and 167.6 K)

Work done = 132.1 kJ and u = -99.2 kJ

q = u + w = 32.9 kJ (heat received from the surroundings and so positive)

Solution
For isothermal expansion, initial temperature = final temperature = 305 .7 K Final pressure can be found from P11= P22 = 0.8775 bar Work done = RT1 ln ( 2 / 1) = 175.7 kJ

u = cvo (T2 T1) = 0 q = u + w = 175.7 kJ

Objective Assessment
Significance of specific heat Calculation of specific heat First law calculations for processes
Only one thing registers on the subconscious mind: repetitive application - practice. What you practice is what you manifest.