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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
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
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
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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
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
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
QT = W
du = -P d and dh = dP For an ideal gas, du = cvodT and dh = cPodT Therefore cvodT = -P d and cPodT = dP
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 / )
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)
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
Objective Assessment
Significance of specific heat Calculation of specific heat First law calculations for processes
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