THERMODYNAMICS

THERMODYNAMICS It is a branch of Science dealing with mechanical action produced by heat. The energy involved may be thermal, chemical, electrical or mechanical energy. CHEMICAL THERMODYNAMICS It is a branch of Thermodynamics which deals with the study of processes in which only chemical energy is involved. CLASSICAL THERMODYNAMICS It deals with macroscopic properties of matter. Here matter is not supposed to be composed of atoms and molecules. STATISTICAL THERMODYNAMICS It is branch of Thermodynamics based on statistical mechanics. Here the matter is composed of atoms and molecules. THERMODYNAMIC SYSTEM Thermodynamic system is a part of universe which is arbitrarily isolated from the rest of the universe by definite boundaries for the purpose of theoretical and experimental studies. SURROUNDINGS The rest of the Universe apart from system is known as surroundings. BOUNDARY The real or imaginary surface separating the system from the surroundings is called boundary.
1

TYPES OF SYSTEM 1. IDEAL SYSTEM It is a system used for theoretical calculations in order to simplify the thermodynamic problems. 2. REAL SYSTEM It is a system used for experimental studies. 3. ISOLATED SYSTEM It is a system which cannot exchange both energy and matter with the surroundings. Eg. A sealed tube containing liquid in equilibrium with its vapour, which is thermally insulated 4. CLOSED SYSTEM It is a system which can exchange energy with the surroundings but not matter. Eg. Liquid in equilibrium with its vapour in a sealed tube 5. OPEN SYSTEM It is a system which can exchange both energy and matter with the surroundings. Eg. Beaker containing water (system) in a thermostated water bath (surroundings) 6. HOMOGENOUS SYSTEM It is a system containing one phase only. Eg. A gas, mixture of gases, pure liquid or two or more miscible liquids 7. HETEROGENOUS SYSTEM It is a system containing more than one phase. Eg. Liquid in contact with vapour, two or more immiscible liquids, two or more solids 8. MACROSCOPIC SYSTEM

It is a system containing a large number of particles. The particles can be atoms, molecules or ions. THERMODYNAMIC PROCESS Changes in values of the properties of the system as it passes from one equilibrium to another are known as thermodynamic process. EXTENSIVE PROPERTIES Properties whose value depends upon the quantity of matter present in the system are known as extensive properties. Eg. Number of moles The total value of the extensive property is the sum total of the separate parts in which the system is subdivided. INTENSIVE PROPERTIES Properties whose value is independent of the quantity of matter present in the system are known as extensive properties. Eg. Refractive Index, Temperature, Density, Surface Tension FIRST LAW OF THERMODYNAMICS 1. Energy can neither be created nor destroyed but can be converted from one form to another. 2. Joules Statement: There is an exact equivalence between the amount of work done and heat absorbed. 3. Maxwells Statement: When work is converted into heat and vice versa, the quantity of heat is mechanically equivalent to work. 4. Energy in an isolated system must remain constant although it can be converted from one form to another. 5. When one form of energy disappears an equivalent amount of another form will appear.
3

6. It is not possible to construct a perpetual motion machine that would produce work without consuming energy. EXPERIMENTAL BASIS FOR FIRST LAW OF THERMODYNAMICS No perpetual motion machine of first kind i.e. a machine that would produce work without consuming energy has been invented. This forms experimental basis for First Law of Thermodynamics. MATHEMATICAL FORMULATION OF FIRST LAW OF THERMODYNAMICS Suppose a system absorbs a quantity of heat q and changes from State A to State B. The heat absorbed is used for increasing the Internal Energy of the System.

E = EB -EA
And to do External Work (W) by the System on the Surroundings. q = E + W

E = q - W
ENTHALPY (H) It is a Thermodynamic parameter which is used in place of Internal Energy while dealing with an Open Vessel process. H = E + PV Where E = Internal Energy V = Volume P = Pressure Since E, P and V are State Functions H is also a State Function.

H = H2 H1
where H1 and H2 represent Initial and Final Enthalpy respectively.

H = E + PV
Change in Enthalpy of a System is defined as amount of heat absorbed at constant pressure provided only work done is of Pressure-Volume type. For a Chemical Reaction:

H = HP HR

where HR and HP represent total reactant and total product Enthalpy respectively. SIGN OF H If HP > HR then H = POSITIVE

ENDOTHERMIC REACTION Heat will be absorbed from the Surroundings. If HP < HR EXOTHERMIC REACTION Heat will be given out to the Surroundings. CHARACTERISTICS OF ENTHALPY 1. It is a State Function 2. For a Cyclic Process Change in Enthalpy is Zero. 3. It in an Extensive Property. HEAT CAPACITY It is a function which relates Heat changes to Temperature changes at constant pressure or constant volume. It is denoted by C. then H = NEGATIVE

HEAT CAPACITY Heat Capacity of a system is defined as the quantity of heat required to raise the temperature of a substance through 1 oC. MOLAR HEAT CAPACITY Heat Capacity of a system is defined as the quantity of heat required to raise the temperature of one mole of a substance through 1 oC.

C=

[dq = dE + PdV]

MOLAR HEAT CAPACITY AT CONSTANT VOLUME (CV) It is defined as the quantity of heat required to raise the temperature of one mole of a substance through 1 oC at constant volume.

Cv = ( )
It is the Rate of change of Internal Energy with temperature at constant volume. MOLAR HEAT CAPACITY AT CONSTANT PRESSURE (CP) It is defined as the quantity of heat required to raise the temperature of one mole of a substance through 1 oC at constant pressure.

CP = ( )
It is the Rate of change of Enthalpy with temperature at constant pressure. RELATION BETWEEN CP and CV

CP Cv = R
WORK Work is product of Force and Displacement If the displacement of a body under force F is dS then dW = F X dS
6

CHARACTERISTICS OF WORK 1. Work is Positive if it is produced in the Surroundings. 2. Work is negative if it is destroyed in the Surroundings. 3. Work appears at the boundary of a System 4. Work appears only during Change of State. 5. Work brings about a Change in the Surroundings. 6. Work is an Algebraic Quantity. TYPES OF WORK 1. GRAVITATIONAL WORK This type of Work is done when a body is raised to a certain height against Gravitational Field. Work = mgh m = Mass of body g = Acceleration due to gravity h = Height 2. ELECTRICAL WORK This type of work is done when a charged body moves from a region of one potential to a region of another potential. Work = Q X V Q = Charge in Coulombs V = Potential in Volts

3. MECHANICAL WORK Work associated with Change in Volume of a system against External Pressure. It is also known as Pressure-Volume Work or PV Work. WORK DONE IN EXPANSION OF AN IDEAL GAS UNDER REVERSIBLE CONDITIONS AT CONSTANT TEMPERTURE Consider reversible expansion of an Ideal Gas from a Volume V1 to Volume V2 at a Constant Temperature T. The Maximum Work done is given as Wmax = For one mole of an Ideal Gas PV = RT

Wmax = Wmax =
For n moles of an Ideal Gas JOULES LAW If a fixed mass of a gas is allowed to expand without doing external work under the condition that no heat enters or leaves the gas. If the molecules of the gas attract one another then internal work will have to be done by the gas pulling them apart. This will happen at the expense of internal kinetic energy of the gas resulting in cooling of the gas. On the other hand if the molecules repel one another then expansion will be accompanied by a rise in temperature.

Wmax =

If there is no intermolecular attraction or repulsion then there will be no change in temperature. JOULE THOMSON EFFECT If a gas under high pressure is allowed to pass through a porous plug to a region of low pressure, its temperature will be lowered. JOULE THOMSON COEFFICIENT It is the rate of change of temperature with pressure at constant enthalpy. THERMOCHEMISTRY It is a branch of Chemistry dealing with heat changes (energy changes) accompanying a chemical reaction. These energy changes are usually absorption or evolution of heat. The energy absorbed could be thermal energy, photo energy and electrical energy. The energy is given out in the form of heat. Thermochemistry is based on First Law of Thermodynamics. A fixed value of energy is associated with a chemical reaction since energy changes are due to breaking of existing bonds and formation of new bonds. THERMOCHEMICAL EQUATION It is an equation which indicates energy changes (evolution or absorption of heat) in a chemical reaction. HEAT OF REACTION OR ENTHALPY OF REACTION

It is the amount of heat absorbed or evolved in the reaction when number of moles of reactants as represented by a balanced chemical equation change completely into products. STANDARD HEAT CHANGE Heat changes accompanying a chemical reaction taking place at 298 K and 1 atmosphere pressure is called a standard heat change or standard enthalpy change. TYPES OF ENTHALPY OF REACTION 1. HEAT OF FORMATION Change in enthalpy when one mole of a compound is formed from its elements. 2. STANDARD HEAT OF FORMATION Change in enthalpy taking place when one mole of a compound is formed from its elements, all substances being in their standard states at 298 K and 1 atmosphere pressure. A. HEAT CHANGES DURING PHASE CHANGES 1. HEAT OF FUSION Heat change (enthalpy change) taking place when one mole of a solid substance gets converted into liquid at its melting point. 2. HEAT OF VAPORISATION Heat change taking place when one mole of a liquid gets converted into vapours at its boiling point.
10

3. HEAT OF SUBLIMATION Heat change taking place when one mole of a solid substance gets converted directly into vapours at a temperature below its melting point. B. HEAT OF TRANSITION Change in enthalpy when one mole of an element changes from one allotropic form to another. C. HEAT OF COMBUSTION Change in enthalpy of a system when one mole of a substance is completely burnt in excess of air or oxygen. D. HEAT OF SOLUTION Change in enthalpy when one mole of a substance is dissolved in a specified quantity of a solvent such that further dilution does not cause any change in enthalpy. E. HEAT OF NEUTRALISATION It is defined as heat change involved when one mole of an acid is neutralized by base or vice-versa in dilute solutions. STANDARD HEAT OF REACTION Standard heat of reaction is the difference between total standard heat of formation of products and total standard heat of formation of reactants.

11

HESS LAW OF CONSTANT HEAT SUMMATION If a same chemical change can take place in two or more different ways whether in one step or more than one step then the amount of heat change is the same for all the ways.

Q = q1 + q2 + q3

RELATION BETWEEN H AND E Consider a reaction aA + bB cC + dD Change in number of moles = Total number of moles of products Total number of moles of reactants = (c + d) (a + b) = n Let the volume occupied by 1 mole be V. Change in volume = n X V Multiplying both sides by P PV = (n) X PV For an Ideal Gas, PV = RT
12

PV = (n) X RT H = E + PV H = E + (n)RT KIRCHOFFS EQUATIONS Kirchoffs Equations represent the variation of heat change of a reaction with temperature. [ ( ) ] ( ) ( ( [ ( ) ] ( ) ( ( ) ) ) )

The above Equations are known as Kirchoffs Equations.

13