Different thermodynamic process and 1st law application in it

 Isochoric process -> Volume remains constant

 dW = 0 => dQ = dU;
 P/T is constant
 P-V curve is a straight line parallel to pressure axis
 Isobaric Process -> Pressure remains constant
 V/T is constant
 W = P(Vf – Vi) = nR(T f – Ti)
 dU = nCv(Tf – Ti)
 Heat supplied dQ = nCp(Tf – Ti)
 P-V curve is a straight line parallel to volume axis
 Isothermal Process -> Temperature constant.
 Molar specific heat is infinite as dT = 0
 dU = 0 for ideal gas
 PV = constant here so P-V curve is hyperbolic
 Slope of P-V curve is dP/dV = –P/V and Bulk modulus of a gas K = P
 W = nRTln(Vf/Vi) = nRTln(Pi/Pf)
 In practice the process is carried out by using diathermic walls and
changing the state of the system very slowly, i.e a quasistatic process.
 Adiabatic Process -> no heat exchange takes place between the system and
the surroundings
 As dQ = 0 => molar specific heat for adiabatic process is zero
 W = (1/( - 1))[PiVi – PfVf] = (nR/(-1))[T i – Tf];  = Cp/Cv
 From 1st law as dU = - dW i.e work done by the system leads to decrease
in internal energy => adiabatic expansion of a gas leads to cooling
 Here PV = constant => TV(-1) = constant => P(1-)T = constant
 Slope of a adiabatic curve = - (P/V) => slope of adiabatic =  x slope of
isothermal i.e adiabatic curve is steeper.
 Bulk modulus K = P.
  The process is carried out by using adiabatic walls and by changing the
state of the system rapidly or fast.
 Adiabatic process is fastest of all four processes.
 Polytropic Process -> Any process which is none of the above standard four
processes.
 General equation is PVx = constant; x 0,1,.
 W = nR(T f – Ti)/(1 – x) = (PfVf – PiVi)/ (1-x)
 Cyclic Process -> System returns to its initial state after a series of operation.
 dU = 0 => dQ = dW
 Efficiency of the cycle is given by  = (Work done/Heat supplied)
 Work done by the cycle is calculated as area enclosed by the cycle in a P-
V curve.
 If cycle is clockwise then W is +ve (i.e by the system) and if
anticlockwise then W is –ve.

Isothermal and Adiabatic Process

For a process to be Isothermal, the requirements are

 The walls of the enclosed cylinder should be perfectly conducting (diathermic

walls)
 The process must be slow
 The equation of state is PV = RT = const as T is constant

To calculate the work done for n mole of ideal gas undergoing expansion/contraction, as
W = PdV from initial volume Vi to final volume Vf => W = (nRT/V)dV = nRTdV/V
=> W = nRTln(Vf/Vi) = nRTln(Pi/Pf) [since PiVi = PfVf]

When a process is Adiabatic then the requirements are

 The walls of the enclosed cylinder should be perfectly insulated (thermally

isolated)
 The process must be quick/fast
  The equation of state is PV = const (=k say), where  = Cp/Cv

Work done for n mole of ideal gas in this case is W = PdV = (k/V)dV = kV-dV
= kV-+1/(1-) = ]k/(-1)][Vi1- – Vf1-]

As k = PiVi = PfVf, so replacing k we get

W = (1/( - 1))[PiVi – PfVf] = (nR/(-1))[T i – T f] as PV = nRT

 Also as PV = constant and PV = nRT, so elminating P from above two we get
TV-1 = const and eleminating V we get P1- .T = const

Adiabatic curve in P-V diagram is steeper than Isothermal Curve

For Isothermal process PV = const => P.1 + V.dP/dV = 0 => dP/dV = -P/V …(i)  the
slope of isothermal process

For adiabatic process PV = const => P.V-1 + V.dP/dV = 0 => dP/dV = -(P/V)…(ii)
 the slope of adiabatic curve

So from eqn (i) and (ii) we get (dP/dV)adi = (dP/dV)iso => slope of adiabatic curve is 
times steeper than isothermal curve as >1 always.
  General Results for different Processes:
 For same initial to final volume expansion Wisobaric>Wisothermal>Wadiabatic
 For same volume compression, work done order is in reverse order as
above
 Two isothermal curve for given mass never intersect each other
 For a given mass, isothermal and adiabatic curve can intersect each
other.
 Bulk Modulus K = - dP/(dV/V) = - VdP/dV
¤ For Isochoric process dV = 0 => K-> 
¤ For Isobaric process dP = 0 => K = 0
¤ For Isothermal process as dP/dV = -P/V => K = P
¤ For Adiabatic process dP/dV = - P/V => K = P

Molar Specific Heat Capacity:

 General relation Cp – Cv = R; Cp/Cv = 

 At constant volume -> Cv = R/( - 1)
 Cp = R/( - 1)
 For a mixture of x number of gases
¤ Cp = (n1Cp1 + n2Cp2 + n3Cp3 +…..nxCpx)/(n1 +n2 +n3 + …. +nx)
¤ Cv = (n1Cv1 + n2Cv2 + n3Cv3 +…..nxCvx)/(n1 +n2 +n3 + …. +nx)
¤ n1, n2, n3, …. Are number of moles in each gas of above
 Adiabatic coefficient () for a mixture is
 = (n1Cp1 + n2Cp2 + n3Cp3 +…..nxCpx)/( n1Cv1 + n2Cv2 + n3Cv3 +…..nxCvx)

Degree of Freedom (f)

 Represents the number of independent possible ways in which the system can
have energy (due to motion or configuration)
 A system can posses energy due to translational, rotational or vibrational motion
or configuration or any combination of these.
 For an ideal monoatomic gas, f = 3 due to translational motion in three direction.
  For an ideal diatomic gas f = 5 due to three translational and two rotational
kinetic energies.
 For ideal polyatomic gas f = 6.
 Cp = (f+2)R/2 and Cv = fR/2 => Cp and Cv values can be obtained depending on
atomicity of the gas.

f=2/(-1);  = 5/3 for monoatomic gas and  = 7/5 for diatomic.