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# Thermodynamics: The branch of science that deals with the study of different forms of energy and the quantitative

relationships between them. System: Quantity of matter or a region of space which is under consideration in the analysis of a problem. Surroundings: Anything outside the thermodynamic system is called the surroundings. The system is separated from the surroundings by the boundary. The boundary may be either fixed or moving. Closed system: There is no mass transfer across the system boundary. Energy transfer may be there. Open system: There may be both matter and energy transfer across the boundary of the system. Isolated system: There is neither matter nor energy transfer across the boundary of the system. State of the system and state variable: The state of a system means the conditions of the system. It is described in terms of certain observable properties which are called the state variables, for example, temperature (t), pressure (p), and volume (v). State function: A physical quantity is a state function in the change in its value during the process depends only upon the initial state and final state of the system and does not depend on the path by which the change has been brought about. Macroscopic system and its properties: If as system contains a large number of chemical species such as atoms, ions, and molecules, it is called macroscopic system. Extensive properties: These properties depend upon the quantity of matter contained in the system. Examples are; mass, volume, heat capacity, internal energy, enthalpy, entropy, Gibb's free energy.Intensive properties: These properties depend only upon the amount of the substance present in the system, for example, temperature, refractive index, density, surface tension, specific heat, freezing point, and boiling point.

Examples: (i) In an ideal monoatomic gas. Isochoric process: It is a process during which the volume of the system is kept constant. the internal energy is in the form of translational. (ii) in a plyatomic gas. Zeroth Law of Thermodynamics When two bodies A and B are separately in thermal equilibrium with a third body C. . Internal energy: It is the sum of all forms of kinetic and potential energy of the system. we call it isothermal. Isothermal process: When the temperature of a system remains constant during a process. Reversible processes: A process which is carried out infinitesimally slowly so that all changes occurring in the direct process can be exactly reversed and the system remains almost in a state of equilibrium with the surroundings at every stage of the process. Isobaric process: It is a process during which the pressure of the system is kept constant. Heat may flow in or out of the system during an isothermal process. rotational and vibrational kinetic energy of the molecules.Types of thermodynamic processes: We say that a thermodynamic process has occurred when the system changes from one state (initial) to another state (final). they are in thermal equilibrium with each other. Adiabatic process: No heat can flow from the system to the surroundings or vice versa. It is the sum of the kinetic energy of motion of the molecules and the potential energy represented by the chemical bonds between the atoms and any other intermolecular forces. the internal energy is in the form of translational kinetic energy of the atoms.

First Law of Thermodynamics Let us consider one of the most fundamental principles of the physical world .It states that energy cannot be created or destroyed. It increases the internal energy of the system. (ii) Heat flowing out of the system is negative. It can be written as U=Q+W Where U is the change in internal energy Q is heat W is work According to this. It decreases the internal energy of the system. let us apply this law to various processes in chemistry. Or we can measure it relative to some arbitrary reference state. We cannot measure the absolute value of internal energy of a system. the internal energy is in the form of translational. It decreases the internal energy of the system. Let us consider the sign convention: (i) Heat flowing into the system is positive. (iii) Work done by the system is positive. there are two kinds of processes that can lead to a change in the internal energy of the system . Now.they are heat and work. rotational and vibrational kinetic energy of the molecules and potential energy associated with the intermolecular attractive forces.The Law of Conservation of Energy . .(iii) In a liquid or solid. The best one can do is measure the changes in internal energy. We use the symbol U for internal energy.

Example Calculate the internal energy change in each of the following cases: (i) A system absorbs 5kJ of heat and does 1kJ of work. we are usually talking about the work done by a gas in expanding. one cannot make out whether this change has come about by adding heat to it or by doing work on it. From a given value of ?U. the interval energy of the system increases. They do depend on the path followed between the initial and final states. System work: When we talk about work done by a thermodynamic system. (i) Work done at constant pressure W=P V It is given by the area under the PV graph (ii) Work done when the pressure is changing W= PdV Note: That work and heat are not state functions. (i) Q = +5kJ W = -1kJ U = Q + W = 5 + (-1) = 4kJ (ii) W = +5kJ Q = -1kJ U = Q + W = -1 + 5 = 4kJ In both the cases. (ii) 5kJ of work is done on the system and 1kJ of heat is given out by the system.Note that: U is a state function. .

W=-P U Q= U . U = U2 .U1) + P(V2 . P and V are functions of state. If pressure is constant.U1 and Substituting we get Q = (U2 . U is the increase in internal energy and W is the work done by the system. H = U + PV Now H2 = U2 + PV2 and H1 = U1 + PV1 Q = H2 + H1 Q= V U = V2 . (U + PV) is called the heat content or enthalpy of the system.V1 . It is represented by symbol H.V1) = (U2 + PV2) .Enthalpy of Heat Content Let us again consider first law of thermodynamics U=Q+W or Q = U-W If Q is the heat absorbed by the system.(-P U) = U+P U If internal energy increases from U1 to U2 and volume increases from V1 to V2 then. thus the quantity U + PV must also be a state function.(U1 + PV1) U1.

5 kJ/mol ----.8 kJ/mol Solution: We have to obtain C(s) + ½O2(g) ? CO(g) Subtracting equation (2) from equation (1) C(s) + O2(g) .(2) ----.Enthalpy change of a system is equal to the heat absorbed or evolved by the system at constant pressure. Hess's law of constant heat summation: The total amount of heat evolved or absorbed in a reaction is the same whether the reaction takes place in one step or in a number of steps.8) = -110.3 kJ/mol (ii) CO(g) + ½O2(g) ? CO2(g) H = -282. the thermo chemical equations can be treated as algebraic equations which can be added.(1) . the total amount of heat exchange in a reaction depends only upon the nature of the initial reactants and the nature of the final products and is independent of the path or the manner by which the change is brought about.3 .CO2(g) C(s) + ½O2(g) ? CO(g) H = -393.393. Thus.½O2(g) . Example: calculate the enthalpy of formation of carbon monoxide (CO) from the following data: (i) C(s) + O2(g) ? CO2(g) H = .CO(g) . subtracted. multiplied or divided. Enthalpy of a substance or a system is the energy stored within the substance or the system that is available for conversion into heat.(-282. In other words.

Entropy is a property which sets the direction of irreversible processes in a closed system. the entropy S of the system always increases. energy and temperature is a property of the state of a system and is independent of how that state is reached.Energy transferred as heat to or from the system during the process. Second law of thermodynamics: S >= 0 In words. It is an irreversible process. Entropy as a state function: Entropy like pressure.5 kJ/mol Entropy and Second Law of Thermodynamics First law gives us an insight into a new property called internal energy. According to the entropy postulate . heat of formation of CO is Hf = 110. Change in entropy: The change in entropy Sf . Heat can never flow from the room back to the soup bowl and heat up the soup again! This flow takes place till equilibrium is attained. Consider a hot bowl of soup in a room.Si of a system during a process that takes the system from an initial state i to a final state f as S = Sf . it never decreases.Thus. . The entropy increases in this process. Second law leads to a new property cal entropy. T . Heat will flow from the bowl to the room till the temperature is equalized.Temperature of the system in Kelvin.If an irreversible process occurs in a closed system.Si = dQ/T where: Q . if a process occurs in a closed system. the entropy of the system increases for irreversible processes and remains constant for reversible processes.

Thus if entropy decreases in one part of the system. Thus. . the total change in entropy is either zero or greater than zero. then it increases by an equal or larger amount in another part of the system.