The first law of thermodynamics

The first law of thermodynamics states that energy can neither be created nor destroyed, although it can be transformed from one form to another. This is also known as the law of conservation of energy.

MATHEMATICAL EXPRESSION OF FIRST LAW

Let UA be the energy of a system in its state A and UB be the energy in its state B. Suppose the system while undergoing change from state A to state B absorbs heat q from the surroundings and also performs some work (mechanical or electrical), equal to w. The absorption of heat by the system tends to raise the energy of the system. The performance of work by the system, on the other hand, tends to lower the energy of the system because performance of work requires expenditure of energy. Hence the change of internal energy, U, accompanying the above process will be given by

U = UB UA = q w

In general, if in a given process the quantity of heat transferred from the surrounding to the system is q and work done in the process is w, then the change in internal energy,

U = q + w

This is the mathematical statement of the first law of thermodynamics.

If work is done by the surroundings on the system (as during the compression of a gas), w is taken as positive so that U = q + w. if however work is done by the system on the surroundings (as during the expansion of a gas), w is taken as negative so that U = q w.

SOLVED EXAMPLE. 1 mole of ideal monoatomic gas at 27C expands adiabatically against a 3 3 constant external pressure of 1.5 atm from a volume of 4dm to 16 dm .

Calculate (i) q (ii) w and (iii) U

Solution:

(i) Since process is adiabatic q = 0

(ii) As the gas expands against the constant external pressure.

W = PV = 1.6(V2V1)

= 1.5 (164) = 18 atm dm

(iii) U = q + w = 0 + (18) = 18 atm dm

Exercise

Calculate the internal energy change, when a system absorbs 5 KJ of heat and does 1 KJ of work.

ENTHALPY OF A SYSTEM

The quantity U + PV is known as the enthalpy of the system and is denoted by H. It represents the total energy stored in the system. Thus

H = U + PV

It may be noted that like internal energy, enthalpy is also an extensive property as well as a state function. The absolute value of enthalpy can not be determined, however the change in enthalpy can be experimentally determined.

H = U + (PV)

Various kinds of processes:

(i) Isothermal reversible expansion of an Ideal gas: Since internal energy of an Ideal gas is a function of temperature and it remains constant throughout the process hence

E = 0 and H = E + PV

E = 0

and P1V1 = P2V2 at constant temperature for a given amount of the gas

H= 0

Calculation of q and w:

E = q + w

For an Isothermal process, w = -q

This shows that in an Isothermal expansion, the work done by the gas is equal to amount of heat absorbed.

and w = - n RT ln(V2/V1) = - n RT ln(P1/P2).

Solved examples.10 gm of Helium at 127C is expanded isothermally from 100 atm to 1 atm Calculate the work done when the expansion is carried out (i) in single step (ii) in three steps the intermediate pressure being 60 and 30 atm respectively and (iii) reversibly.

Solution:

(i) Work done = V.P

V = (10/4) 8.314400 / 100 10 = 83.14 10

So W = 8314/10 (100-1) 10 = 8230.86 J.

(ii) In three steps

VI = 83.1410 m

-5

W I = (83.1410 )(100-60)10

-5

= 3325.6 Jules

VII = 2.5 8.314 400 / 60 10 = 138.56 10 m

W II = V. P

W II = 138.5610 (60-30)10

-5

= 4156.99 4157 J.

VIII = 2.5 8.314 400 / 30 10 = 277.13 10

W III = 277.1310 (30-1)10

-5

W III =8036.86 J.

total =

W I + W II + W III

= 3325.6+4156.909+8036.86 = 15519.45 J.

(iii)

For reversible process

W = 2.303 nRT log P1/P2

= 2.303 (10/4) 8.314 400 log (100/1)

W = 38294.28 Jules

Exercise .

Calculate the final volume of one mole of an ideal gas initially at 0C and 1 atm pressure, if it absorbs 1000 cal of heat during a reversible isothermal expansion.

Exercise .

Carbon monoxide is allowed to expand isothermally and reversibly from 10m to 20 m at 300 K and work obtained is 4.754 KJ. Calculate the number of moles of carbon monoxide.

(ii)

Adiabatic Reversible Expansion of an Ideal gas:

q=0

E= -w.

Total change in the internal energy is equal to external work done by the system.

Work done by the system = E= CvT.

and Cp-Cv = R

On dividing all the terms by Cv.

Cp/Cv Cv/Cv R/Cv

Cp/Cv =

( 1) = R/Cv

and Cv = R / ( 1)

and = R / ( 1) (T2 T1) H = E + PV.

Thus if T2>T1, w = +ve i.e. work is done on the system.

Thus if T2<t1, w = -ve i.e. work is done by the system.</t

Limitations of the first law. Need for the second law

A major limitation of the first law of thermodynamics is that its merely indicates that in any process there is an exact equivalence between the various forms of energies involved, but it provides no information concerning the spontaneity or feasibility of the process. For example, the first law does not indicate whether heat can flow from a cold end to a hot end or not.

The answers to the above questions are provided by the second law of thermodynamics.

Spontaneous and non spontaneous process

If in the expansion of a gas the opposing pressure is infinitesimally smaller than the pressure of the gas, the expansion takes place infinitesimally slowly i.e. reversible. If however, the opposing pressure is much smaller than the pressure of the gas the expansion takes place rapidly i.e. irreversibly. Natural processes are spontaneous and irreversible.