11.3 ZEROTH LAW OF THERMODYNAMICS (a) Imagine two systems A and B, separated by an adiabatic wall, while each is in contact with a third system C, via a conducting wall [Fig. 11.2(a)]. The states of the systems (i.e., their macroscopic variables) will change until both A and B come to thermal equilibrium with C. After this is achieved, suppose that the adiabatic wall between A and B is replaced by a conducting wall and C is insulated from A and B by an adiabatic wall [Fig.11.2(b)]. It is found that the states of A and B change no (b) further i.e. they are found to be in thermal Fig. 11.2 (a) Systems A and B are separated by an equilibrium with each other. This observation adiabatic wall, while each is in contact forms the basis of the Zeroth Law of with a third system C via a conducting Thermodynamics, which states that ‘two wall. (b) The adiabatic wall between A systems in thermal equilibrium with a third and B is replaced by a conducting wall, system separately are in thermal equilibrium while C is insulated from A and B by an adiabatic wall.with each other’. R.H. Fowler formulated this * Both the variables need not change. It depends on the constraints. For instance, if the gases are in containers of fixed volume, only the pressures of the gases would change to achieve thermal equilibrium. Reprint 2025-26 THERMODYNAMICS 229

11.2 THERMAL EQUILIBRIUM independent variables. Let the pressure and Equilibrium in mechanics means that the net volume of the gases be (PA, VA) and (PB, VB) external force and torque on a system are zero. respectively. Suppose first that the two systems The term ‘equilibrium’ in thermodynamics appears are put in proximity but are separated by an * Thermodynamics may also involve other variables that are not so obvious to our senses e.g. entropy, enthalpy, etc., and they are all macroscopic variables. However, a thermodynamic state is specified by five state variables viz., pressure, volume, temperature, internal energy and entropy. Entropy is a measure of disorderness in the system. Enthalpy is a measure of total heat content of the system. Reprint 2025-26 228 PHYSICS adiabatic wall – an insulating wall (can be law in 1931 long after the first and second Laws movable) that does not allow flow of energy (heat) of thermodynamics were stated and so numbered. from one to another. The systems are insulated The Zeroth Law clearly suggests that when two from the rest of the surroundings also by similar systems A and B, are in thermal equilibrium, adiabatic walls. The situation is shown there must be a physical quantity that has the schematically in Fig. 11.1 (a). In this case, it is same value for both. This thermodynamic found that any possible pair of values (PA, VA) will variable whose value is equal for two systems in be in equilibrium with any possible pair of values thermal equilibrium is called temperature (T ). (PB, VB). Next, suppose that the adiabatic wall is Thus, if A and B are separately in equilibrium replaced by a diathermic wall – a conducting wall with C, TA = TC and TB = TC. This implies that that allows energy flow (heat) from one to another. TA = TB i.e. the systems A and B are also in It is then found that the macroscopic variables of thermal equilibrium. the systems A and B change spontaneously until We have arrived at the concept of temperature both the systems attain equilibrium states. After formally via the Zeroth Law. The next question that there is no change in their states. The is : how to assign numerical values to situation is shown in Fig. 11.1(b). The pressure temperatures of different bodies ? In other words, and volume variables of the two gases change to how do we construct a scale of temperature ? (PB ′, VB ′) and (PA ′, VA ′) such that the new states Thermometry deals with this basic question to of A and B are in equilibrium with each other*. which we turn in the next section. There is no more energy flow from one to another. We then say that the system A is in thermal equilibrium with the system B. What characterises the situation of thermal equilibrium between two systems ? You can guess the answer from your experience. In thermal equilibrium, the temperatures of the two systems are equal. We shall see how does one arrive at the concept of temperature in thermodynamics? The Zeroth law of thermodynamics provides the clue.

3.22 The rate constant for the decomposition of N2O5 at various temperatures is given below: T/°C 0 20 40 60 80 105 × k/s-1 0.0787 1.70 25.7 178 2140 Draw a graph between ln k and 1/T and calculate the values of A and Ea. Predict the rate constant at 30° and 50°C.