- 2. Paper 8: Physical Chemistry 1. Thermodynamics - I 15 hrs. Definition: of Thermodynamic Terms: System, Surrounding types of system, intensive and extensive properties. Thermodynamic Process, Concept of heat and work. Work done in reversible and irreversible process, concept of maximum work (Wmax), Numerical Problems. First law of Thermodynamics: Statement, Definition of Internal energy and Enthalpy. Heat capacity, heat capacities at constant volume pressure and their relationship. Calculation of W, q, dU and dH for the expansion of ideal gases under isothermal and adiabatic conditions for reversible process, Numerical problems, Hessβs law of heat Summation and its application. 2. Thermodynamic - II 20 hrs. Second Law of Thermodynamics: Need for the law, different statement of the law Carnot Cycle and its efficiency, Numerical Problems. Carnot Theorem. Concept of Entropy: Definition, Physical significance, Entropy as a State Function, Entropy change in Physical change, Entropy as criteria of Spontaneity & Equilibrium Entropy Change in Ideal Gases. Gibbs and Helmholtz Functions: Gibbs Function (G) and Helmoltz Function (A) as Thermodynamic Quantities. A and G as criteria for Thermodynamic Equilibrium and Spontaneity, their Advantage over Entropy change. Variation of A with P, V and T. 3. Chemical Equilibrium 10 hrs. Equilibrium Constant and Free Energy. Thermodynamic Derivation of Law of Mass Action. Le Chatelierβs Principle. Reaction Isotherm and Reaction Isochore. Clapeyron Equation, Clausius-Clapeyron Equation and its Application.
- 3. Thermodynamics Thermodynamics is the study of energy. OR Thermodynamics is the study of the movement of heat from one body to another and the relations between heat and other forms of energy. OR Thermodynamics is the study of the connection between heat and work and the conversion of one into the other. OR Chemical thermodynamics is the study of energy relationships in chemistry.
- 4. Why is the study of Thermodynamics important? The study of thermodynamics is important because- many machines and modern devices change heat into work, such as an automobile engine or turn work into heat or cooling, such as with a refrigerator. How the conversion of energy from one from to another, change in state, change in matter etc occurs.
- 5. Different forms of energies οΆ Kinetic Energy : Having motion οΆ Potential Energy : Have βpotentialβ οΆ Chemical Energy : Free energy of chemical sub. οΆ Thermal Energy : Function of temperature οΆ Nuclear Energy : Unstable nuclei (Binding energy) οΆ Molecular Energy: Translational, rotational, vibrational and electronic energy.
- 6. β’ Kinetic Energy: β Consider a baseball flying through the air. The ball is said to have "kinetic energy" by virtue of the fact that its in motion relative to the ground. β’ Potential Energy: β Consider a book sitting on a table. The book is said to have "potential energy" because if it is nudged off, gravity will accelerate the book, giving the book kinetic energy. Therefore, it has βpotential.β β’ Thermal or Heat Energy: β Consider a hot cup of coffee. The coffee is said to possess "thermal energy", or "heat energy," which is really the collective, microscopic, kinetic, and potential energy of the molecules in the coffee. This energy is function of temperature. Chemical Energy: Consider the ability of your body to do work. The glucose (blood sugar) in your body is said to have "chemical energy" because the glucose releases energy when chemically reacted (combusted) with oxygen.
- 7. Electrical Energy All matter is made up of atoms, and atoms are made up of smaller particles, called protons, neutrons, and electrons. Electrons orbit around the center, or nucleus, of atoms, just like the moon orbits the earth. The nucleus is made up of neutrons and protons. Material, like metals, have certain electrons that are only loosely attached to their atoms. They can easily be made to move from one atom to another if an electric field is applied to them. When those electrons move among the atoms of matter, a current of electricity is created. Electrochemical Energy: Consider the energy stored in a battery. Like the example above involving blood sugar, the battery also stores energy in a chemical way. But electricity is also involved, so we say that the battery stores energy "electro-chemically". Another electron chemical device is a "fuel-cell". Sound Energy: Sound waves are compression waves associated with the potential and kinetic energy of air molecules. When an object moves quickly, for example the head of drum, it compresses the air nearby, giving that air potential energy. That air then expands, transforming the potential energy into kinetic energy (moving air). The moving air then pushes on and compresses other air, and so on down the chain. Electromagnetic Energy (light): E = hΞ½ Nuclear Energy: E = 931.1 Ξm
- 8. 1) The most obvious and trivial way in which energy is transported is when an object that possesses energy simply moves from one place to another. For example, a baseball flying through the air is a simple form of energy transport. 2) Kinetic energy can also be transferred from one object to another when objects collide. This is also pretty trivial, except that we also know that the total energy, including any heat or other forms of energy generated during the collision, is conserved in this process, regardless of the relative sizes, shapes, and materials of the objects. 3) There are three important ways that heat energy can be transported or transferred, called conduction, convection, and radiation. The first two refer to transfer of the thermal energy, whereas the last is really a conversion of energy to a different form, (photons of light) and the subsequent travel (transport) of those photons. 11/26/2021 8 How is energy transported from place to place and transferred between objects?
- 9. 4) The "diffusion" of thermal energy (heat) through a substance, which occurs because hotter molecules (those that are vibrating, rotating, or traveling faster), interact with colder molecules, and in the process transfer some of their energy. Metals are excellent conductors of heat energy, whereas things like wood or plastics are not good conductors of heat. Those that are not so good conductors are called insulators. 5) The transfer of heat energy by the movement of a substance, such as a heated gas or liquid from one place to another. For example, hot air rising to the ceiling is an example of convection (in this case called a convection current). 6) In the context of heat transfer, however, the term βemits radiation" refers just to light (electro-magnetic waves), and in particular, to the surprising fact that all objects, even those that are in equilibrium (at equal temperature) with their surroundings, continuously emit, or radiate electromagnetic waves (that is, light waves) into their surroundings. The source of this radiation is the thermal energy of the materials, that is, the movement of the object's molecules. 11/26/2021 9
- 11. SOME TERM USED IN THERMODYNAMICS βThe part of universe that under study in thermodynamics is called as system, it is real or imaginary.β βThe Remaining part of the universe which is in contact or interacts with the system is called as surrounding.β For the thermodynamic study the interaction between system and surrounding is very important. According to the interaction (exchange of matter and energy), systems are classified in as: 1) Open system:- A system which can exchange both matter and energy with itβs surrounding is called as open system. e.g.- Heating of water in open beaker. 2) Closed system:- A system which exchange only energy but not matter with itβs surrounding is called as closed system. e.g.- Heating of water in closed/sealed container. 3) Isolated system:- A system which neither exchange energy nor the matter with itβs surrounding is called as isolated system. e.g.- Store of hot water in thermos flask. The systems were further classified according to the phases as- homogeneous and heterogeneous system. Phase of the system is defined as - a homogeneous, physically distinct and mechanically separable portion of a system.
- 12. β’ According to the nature of the changes occurs in the system, it may be reversible and irreversible, system can be classified as reversible and irreversible system. β’ βChemical changes in which driving and opposing forces are differ by large amount in which driving force large than opposing force, if opposing force increased by small amount, reaction does not reverse is called as irreversible process.β β’ βA reaction proceeds in only one direction is called as irreversible reaction while the reaction proceeds in both directions is called as reversible reactionβ. βA chemical reaction in which driving and opposing forces are differ by infinitely small amount and proceeds till attends equilibrium state, if opposing force is increased by small amount, reaction become reverse is called as reversible reaction. Substitution reaction
- 13. The properties of the system are classified into two groups as- a) Extensive properties:- An extensive properties of the system is any property whose magnitude is depends on the amount of present in the system. e.g.- pressure, volume, entropy, free energy, etc. b) Intensive properties:- Intensive properties of a system is any property whose amount is independent on the total amount but depends on the concentration of the substance or substances in a system. e.g.- density, refractive index, chemical potential, viscosity, surface tension, etc. Properties of system System Properties depends on amount Properties independs on amount Extensive properties Intensive properties
- 15. β’ According to the process occurring in the system or according to the fundamental parameter change in a system, it can be classified as- β’ 1) Isothermal process:- A process occurring at constant temperature is called as isothermal process and a system is called as isothermal system. Ξ T = 0 β’ 2) Isobaric process:- A process occurring at constant pressure is called as isothermal process and a system is called as isobaric system. Ξ P = 0 β’ 3) Isochronic process:- A process occurring at constant volume is called as isothermal process and a system is called as isochronic system. Ξ V = 0 β’ 4) Cyclic process:- A process in which a change in any state function such as internal energy is equal to zero or a process in system having initial and final state are same is called as cyclic process and system is called as cyclic system. Change in state function = 0 β’ 5) Adiabatic process:- A process in which system does not exchange heat with itβs surrounding is called as adiabatic process and a system is adiabatic system. q = 0. β’ All fundamental parameters or properties (P, V, T, H, E, G, A, density, surface tension, K, etc) are classified into two types as- β’ a) State function:- A parameter or properties of the system is depends on only initial and final state of the system but not on the path through which change occurs is called as state function. β’ e.g.- free energy, entropy, pressure, volume, etc. β’ b) Path function:- A parameter or properties of the system is depends on the path through which change occurs but not on the initial and final state of the system is called as path function.
- 16. The First law of Thermodynamics -energy cannot be created or destroyed only converted from one form to another. -Energy can be changed from one form to another, but it cannot be created or destroyed. -The total amount of energy and matter in the Universe remains constant, merely changing from one form to another. -The First Law of Thermodynamics (Conservation) states that energy is always conserved, it cannot be created or destroyed.
- 17. The First law of Thermodynamics The supplied heat is converted to work and change in internal energy, work and internal energy are forms of energy transfer and hence energy is conserved. change in total internal energy heat added to system State Function Process Functions οE = q + Won
- 18. system done work : positive system added heat : positive by to W q W q E ο ο½ ο The First law of Thermodynamics β’ statement of energy conservation for a thermodynamic system β’ internal energy E is a state variable β’ W, q process dependent
- 19. Sign conventions: (a) Heat: ο q is positive - heat is flow from surrounding to the system i.e. system absorb heat from surrounding. ο q is negative - heat is flow from system to the surrounding i.e. system lost heat to its surrounding. (b) Work done: ο System does work on its surrounding, W is positive. ο Surrounding does work on its System, W is negative. (c) Internal energy: ο Both heat (q) and Work done (W) is positive, internal energy of the system increase i.e. ΞE increases. ο Internal energy of the system decreases, ΞE is negative.
- 20. . 11/26/2021 20 The First Law of Thermodynamics by dW dq dE ο ο½ int What this means: The internal energy (dE) of a system tends to increase if energy is added via heat (dq) and decrease via work (dW) done by the system. on dW dq dE ο« ο½ int . . . and increase via work (W) done on the system. on by dW dW ο ο½
- 27. Work done in reversible and irreversible process: Consider a cylinder having cross-sectional area βAβ fitted with weightless and frictionless piston. Let pressure of gas on the piston is βpβ (p = f/A) and the force acting on the piston is βfβ. For reversible isothermal expansion, piston moves in upward direction through a distance dl so that the volume change is dV and the pressure (p β dp). dw = (p β dp) dV = pdV β dp.dV 1 But for reversible expansion, change in pressure and volume is very small, so that dp.dV β 0 (neglected) dw = p.dV 2 For one mole of ideal gas - pV = RT or p = RT/V 3 From equation (2) and (3), dw = RT. (dV/V) Integrate this equation with the limits V1 to V2 at constant temperature, we have: ππ€ = π π π1 π2 ππ π π = π π ln π2 β ln π1 π = 2.303 π π log π2 π1 For n mole of ideal gas: π = 2.303 ππ π log π2 π1 At constant temperature, according to the Boyleβs law: p.V = Constant. π1π1 = π2π2 or π2 π1 = π1 π2 Where, P1, V1 is the initial pressure and volume and P2, V2 is the final pressure and volume of the system respectively. π = 2.303 ππ π log π1 π2
- 28. The workdone is maximum, when opposing pressure βPβ differs only infinitesimally small (dp) in magnitude from the internal pressure of the gas itself which is the condition for the reversibility of the reaction. π πππ₯ = 2.303 π π log π2 π1 = 2.303 ππ π log π1 π2 In reversible expansion In reversible compression π πππ₯ = 2.303 π π log π1 π2 = 2.303 ππ π log π2 π1 For irreversible process: The gas was expand irreversibly from volume V1 toV2 at constant pressure P and temperature T, then from equation (1)- dw = p . dV On integration between the limits V1 and V2, π = π π1 π2 ππ π = PΞV
- 29. Enthalpy The thermal changes at constant pressure can be expressed by using new thermodynamic function called as enthalpy (H). βIt is sum of internal energy (E) of the system and pressure-volume product (PV).β Since E and PV are the state functions of the system, H is also state function. Therefore change in enthalpy can be determined as: ΞH = H2 - H1 H2 and H1 are enthalpies of the final and initial state of the system: H1 = E1 + P1V1 H2 = E2 + P2V2 and ΞH = H2 - H1 = (E2 + P2V2) β (E1 + P1V1) = (E2- E1) + (P2V2- P1V1) = ΞE + ΞPV At constant pressure, ΞH = ΞE + PΞV For an ideal gas: PV = nRT At constant P and T, PΞV = Ξn RT (Ξn is change in number of moles during the reaction) ΞH = ΞE + Ξn RT According to the first law of thermodynamics: q = W + ΞE And workdone by irreversible process at constant P is: W = PΞV, therefore β q = ΞE + PΞV Therefore, change in enthalpy - ΞH = q
- 30. Heat capacity A small amount of heat is added to a system, causes rise in temperature. Suppose a small amount of heat (dq) required to rising the temperature of the system by one degree is called as heat capacity. Heat capacity = ππ dT Heat capacity does not explain amount of the system therefore new term is used containing amount of matter is called as molar heat capacity. βThe amount of heat (dq) required to rise the temperature of the one mole of the gas through one degree is called as molar heat capacity.β It is denoted by latter C. C = ππ dT But according to the first law of thermodynamics: dq = dE + PdV C = (dE + PdV) dT The molar heat capacity at constant volume is called as (Cv). dV = 0 πΆπ£ = ππΈ dT π At constant volume, the amount of heat (dq) required to rise the temperature of the one mole of the gas through one degree is called as molar heat capacity at constant volume (Cv). At constant pressure, the heat absorbs ΞH = q. the molar heat capacity at constant pressure is called as Cp. πΆπ = ππ dT = ππ» dT π At constant pressure, the amount of heat (dq) required to rise the temperature of the one mole of the gas through one degree is called as molar heat capacity at constant pressure (Cp).
- 31. Difference between two heat capacities is - Cp - Cv = ππ» dT π - ππΈ dT π But according to the definition of enthalpy, H = E + PV. Differentiate it with respect to temperature at constant pressure, then- ππ» dT π = ππΈ dT π + P ππ dT π But the internal energy E is the function of any two of the three variables; P, V and T. If V and T are two independent variables, then; E = f(V,T) dE = ππΈ dT π dT + ππΈ dV π dV Dividing both side by dT and apply the condition of constant pressure as: ππΈ dT π = ππΈ dT π + ππΈ dV π ππ dT π Cp - Cv = ππΈ dT π + ππΈ dV π ππ dT π + P ππ dT π - ππΈ dT π = ππΈ dV π ππ dT π + P ππ dT π For an ideal gas PV = nRT, differentiate it with respect to T at constant V gives; ππ dT π = ππ π But, ππΈ dV π = π ππ dT π β π ππΈ dV π = π ππ π β P = P β P = 0. The internal energy of the ideal gas is independs on the volume
- 32. The internal energy of the ideal gas is depends on the volume, but it depends on temperature. If we differentiate ideal gas equation with respect to temperature at constant pressure, then- ππ dT π = ππ π But, ππ» dP π = V β T ππ dT π ππ» dP π = V β T ππ π = V β V = 0 Enthalpy of an ideal gas is independent on the pressure Cp - Cv = ππΈ dT π + P ππ dT π - ππΈ dT π = P ππ dT π From the above explanation, a conclusion is drawn that Cp and Cv are functions of T only and is independent on volume and pressure. But for ideal gas; PV = RT (for one mole) Therefore, P ππ dT π = R. Cp - Cv = R For n moles of ideal gas; Cp - Cv = nR
- 33. Alternative derivation: According to definition of enthalpy - H = E + PV 1 For one mole of ideal gas - PV = RT 2 From (2), equation (1) become - H = E + RT 3 Differentiate (3) completely - dH = dE + R dT 4 From the definition of Cp & Cv Cp dT = Cv dT + R dT Devided both side by dT - Cp - Cv = R For n moles of ideal gas; Cp - Cv = nR
- 34. Adiabatic process in ideal gases In an adiabatic process, there is no exchange of heat between a system and itβs surrounding i.e. q = 0. According to the first law of thermodynamic - ΞE = -W Work is done by the system decreases internal energy and therefore temperature of the system. For infinitesimally small increase in volume dV at constant pressure P, the workdone is PdV. This workdone is due to expense of internal energy of the gas. The decrease in internal energy is dE. dE = -P dV But according to the definition of Cv: dE = Cv dT for one mole of gas. Cv dT = -PdV According to the ideal gas equation- PV = RT or P = RT/V πΆπ£ ππ = β π π π ππ ππ π = β πΆπ£ π ππ π Consider Cv is constant and integrate above equation with the limits V1 at T1 and V2 at T2, we have: π1 π2 ππ π = β πͺπ πΉ π1 π2 ππ π ln π2 π1 = β πΆπ£ π ln π2 π1 ln π2 π1 = ln π2 π1 β πΆπ£ π ln π2 π1 = ln π1 π2 πΆπ£ π
- 35. ln π2 π1 = ln π1 π2 πΆπ£ π Taking antilog of both sides, we have: π2 π1 = π1 π2 πΆπ£ π or π1π1 πΆπ£ π = π2π2 πΆπ£ π Where, Cv is constant. According to the Boyleβs law: PV = constant or V1P1 = V2P2 or π2 π1 = π1 π2 π1 π2 = π1 π2 πΆπ£ π π1 π1 πΆπ£ π = π2 π2 πΆπ£ π According to the ideal gas equation- PV = RT (for one mole of ideal gas). T = π π π π1 π1π1 π πΆπ£ π = π2 π2π2 π πΆπ£ π π1 πΆπ£+π π π1 πΆπ£ π = π2 πΆπ£+π π π2 πΆπ£ π π1 πΆπ π π1 πΆπ£ π = π2 πΆπ π π2 πΆπ£ π because Cp - Cv = R Taking Rth power of both side, π1 πΆπ π1 πΆπ£ = π2 πΆπ π2 πΆπ£ = constant. Taking Cv th root of both side, π1 πΆπ πΆπ£ π1 = π2 πΆπ πΆπ£ π2 = constant. Put (Cp/Cv) = Ξ³ i.e. ratio of molar heat capacities at constant pressure and constant volume respectively. π1π 1 πΎ = π2π 2 πΎ
- 36. The workdone performed in the adiabatic reversible expansion of ideal gas as: Differentiate PVΞ³ = constant completely. πΎ π ππΎβ1ππ + ππΎππ = 0 Dividing both side by VΞ³-1: Ξ³ PdV + V.dP = 0 V.dP = -Ξ³ PdV Differentiate the equation PV = nRT completely, we have- PdV + VdP = nRdT (1-Ξ³) PdV = nRdT or π ππ = π π ππ 1 β πΎ The work done: dW = PdV = π π ππ 1βπΎ Integrate equation with the limits of temperature T1 and T2 as: T2 Wm = β« nRdT/(1-Ξ³) = [nR/(1-Ξ³)](T2- T1) T1 If T2 > T1, Ξ³ > 1, then, Wm is negative, i.e. work is done on the gas/system. If T2 < T1, Ξ³ > 1, then Wm is positive, i.e. work is done by the gas.
- 37. Hessβs law of heat Summation and its application If a reaction takes place in several steps then its standard reaction enthalpy is the sum of the standard enthalpies of the intermediate reactions into which the overall reaction may be divided at the same temperature. enthalpy is a state function Enthalpy of an overall reaction A β B along one route is βrH βrH = βrH1 + βrH2 + βrH3 + .....
- 38. Example: Given the thermochemical equations: 2 WO2 (s) + O2 (g) β 2 WO3 (s) οH = -506 kJ 2 W(s) + 3 O2 (g) β 2 WO3 (s) οH = -1686 kJ Calculate the enthalpy change for: 2 W(s) + 2 O2 (g) β 2WO2 (s).
- 39. Hessβs law of heat Summation and its application Standard enthalpy of combustion (symbol: βcH*) Combustion reactions are exothermic in nature Important in industry, rocketry, and other walks of life βthe enthalpy change per mole (or per unit amount) of a substance, when it undergoes combustion and all the reactants and products being in their standard states at the specified temperatureβ. Cooking gas in cylinders contains mostly butane (C4H10) which completely burns release 2658 kJ of heat. C4H10 (g) + 13/2 O2 (g) β 4CO2 (g) + 5H2O(1); βcH* = - 2658 kJ mol-1. Combustion of glucose gives out 2802.0 kJ/mol of heat C6H12O6 (g) + 6O2 (g) β 6CO2 (g) + 6H2O(1); βcH* = - 2802.0 kJ mol-1
- 40. Enthalpies of Formation An enthalpy of formation, ΞHf, is defined as the enthalpy change for the reaction in which a compound is made from its constituent elements in their elemental forms. Standard Enthalpy of Formation The standard enthalpy of formation is the enthalpy change when one mole of a substance in its standard state is formed from the most stable form of the elements in their standard states. Enthalpy of atomization (symbol: βΞ±H*) It is the enthalpy change on breaking one mole of bonds completely to obtain atoms in the gas phase. In case of diatomic molecules, like dihydrogen, the enthalpy of atomization is also the bond dissociation enthalpy. H2 (g) β 2H (g); βΞ±H* = 435.0 kJ molβ1
- 41. Bond Enthalpy (symbol: βbondH*) Energy is required to break a bond and energy is released when a bond is formed. The enthalpy changes associated with chemical bonds, two different terms are used in thermodynamics. (i) Bond dissociation enthalpy The bond dissociation enthalpy is the change in enthalpy when one mole of covalent bonds of a gaseous covalent compound is broken to form products in the gas phase. (ii) Mean bond enthalpy Mean of energy required to break the similar bonds. The net enthalpy change of a reaction is the amount of energy required to break all the bonds in the reactant molecules minus the amount of energy required to break all the bonds in the product molecules. CH4 (g) β CH3 (g) + H (g); βC-HH* = 427 kJ mol-1 CH3 (g) β CH2 (g) + H (g); βC-HH* = 439 kJ mol-1 CH2 (g) β CH (g) + H (g); βC-HH* = 452 kJ mol-1 CH (g) β C (g) + H (g); βC-HH* = 347 kJ mol-1 Therefore, CH4 (g) β C (g) + 4H (g); βΞ±H* = 1665 kJ mol-1 βCβHH* = ΒΌ (βΞ±H*) = ΒΌ (1665 kJ mol-1) = 416 kJ mol-1 Mean bond enthalpy
- 42. Enthalpy of Solution (symbol: βsolH*) The enthalpy of solution at infinite dilution is the enthalpy change observed on dissolving the substance in an infinite amount of solvent when the interactions between the ions (or solute molecules) are negligible. The enthalpy of solution of AB(s), βsolH*, in water βsolH* = βlatticeH* + βhydH* Lattice Enthalpy The lattice enthalpy of an ionic compound is the enthalpy change which occurs when one mole of an ionic compound dissociates into its ions in gaseous state. It is impossible to determine lattice energies directly by experiment hence we use an indirect approach to determine it by constructing energy diagram called a Born-Haber cycle.
- 43. Na+ (g) + Cl (g) Na+ (g) + Cl- (g) NaCl(s) Na (g) + Cl (g) Na (g) + 1/2Cl2 (g) Na (s) + 1/2Cl2 (g) - 348.8 kJ -787.0 kJ - 4 1 1 . 3 k J +107.8 kJ +121.3 kJ +495.4 kJ Lattice energy Ionization energy of Na (g) D i r e c t p a t h Electron affinity of Cl(g) energy needed to form gaseous Cl atoms energy needed to form gaseous Na atoms Heat of formation of NaCl
- 44. A metal pellet with mass 100.0 g, originally at 88.4 0C, is dropped into 125 g of water originally at 25.1 0C. The final temperature of both the pellet and the water is 31.3 0C. Calculate the heat capacity C (in J/0C) and specific heat capacity Cs (in J/gο0C) of the pellet. The specific heat of water is 4.184 J/g.0C. Two litres of an ideal gas at a pressure of 10 atm expands isothermally into a vacuum until its total volume is 10 litres. How much heat is absorbed and how much work is done in the expansion? If water vapour is assumed to be a perfect gas, molar enthalpy change for vapourisation of 1 mol of water at 1bar and 100Β°C is 41 kJ molβ1. Calculate the internal energy change, when (i) 1 mol of water is vaporised at 1 bar pressure and 100Β°C. (ii) 1 mol of water is converted into ice.
- 45. 1g of graphite is burnt in a bomb calorimeter in excess of oxygen at 298 K and 1 atmospheric pressure according to the equation: C (graphite) + O2 (g) β CO2 (g) During the reaction, temperature rises from 298 K to 299 K. If the heat capacity of the bomb calorimeter is 20.7kJ/K, what is the enthalpy change for the above reaction at 298 K and 1 atm?
- 46. Carnot Cycle Carnot heat engine is an ideal engine operating under ideal conditions. Convert a fraction of absorbed heat into work. Operating between the temperatures T1 (source) and T2 (sink) (T1 > T2). Absorb a quantity of heat at some temperature T1, Convert a part of heat into work, and remaining part of heat is rejected at temperature T2. Carnot by considering a sequence of operations called as Carnot cycle (series of operations so conducted and at the end; the system is back to its original state). cylinder fitted with weightless and frictionless piston, It containing a given substance (gas) is called as working substance. insolating jacket used to perform adiabatic process a source having temperature T1 and supplied heat to the working substance sink having temperature T2 and act as heat acceptor
- 49. A Carnot cycle operates in four different steps- two are isothermal and two are adiabatic process A(P4 ,V4 ) B(P1 ,V1 ) C(P2 ,V2 ) D(P3 ,V3 ) q1 q2 T1 T2 Wm P V Isothermal reversible expansion Isothermal reversible compression I. I II III IV III. II. Adiabatic reversible expansion IV. Adiabatic reversible Compression 1. The pressure, volume and temperature of the working substance is P4, V4, and T1 at point A. A substance absorbs heat from source q1 at the temperature T1 and undergoes isothermal and reversible expansion to a point B having pressure P1 and volume V1. The change in internal energy is ΞE1 and work done is W1. According to the first law of thermodynamics: ΞE1 = q1 - W1. 1 And πΎπ = ππΉπ»π ππ π½π π½π
- 50. 2) Expand gas adiabatically and reversibly from point B (P1, V1, T1) to a point C (P2, V2, T2). For the adiabatic process, q = 0, the work done by the system is W2 at the expense of an internal energy ΞE2. During the expansion temperature must be drop from T1 to T2. 4) Expand gas adiabatically and reversibly from point D (P3, V3, T2) to a point A (P4, V4, T1). For the adiabatic process, q = 0, the work done by the system is W4 at the expense of an internal energy ΞE4. During the expansion temperature must be drop from T2 to T1. According to the first law of thermodynamics: ΞE2 = - W2. 2 And, π2 = π π1 π2 πΆπ£ ππ π ΞE4 = - W4. 4 And π4 = π π2 π1 πΆπ£ ππ π According to the first law of thermodynamics: 3) Gas is compressed isothermally and reversibly at temperature T2 from a point C (P2, V2) to D (P3, V3). During this step, work done on the gas (system) is W3, a quantity of heat given to sink or surrounding is q2. According to the first law of thermodynamics: ΞE3 = - W3 β q2 3 And π3 = ππ π2 ln π3 π2
- 51. For complete cycle, the total change in internal energy is- ΞE = ΞE1 + ΞE2 + ΞE3 + ΞE4 = q1 - W1 β W2 β q2 β W3 β W4. = (q1 β q2) β (W1 + W2 + W3 + W4) = (q1 β q2) β Wm Wm is the total work done by the gas in the one complete cycle. The principle of reproducibility of the states for cycle or reversible process, ΞE = 0. E is state function. Wm = (q1 β q2) 5 = (W1 + W2 + W3 + W4) = ππ π1 ln π1 π4 + π π1 π2 πΆπ£ ππ π + ππ π2 ln π3 π2 + π π2 π1 πΆπ£ ππ π = ππ π1 ln π1 π4 + ππ π2 ln π3 π2 6
- 52. But the point B(P1,V1) at T1 and point C(P2,V2) at T2 are lie on same adiabatic curve BC. π1π1 πΆπ£ π = π2π2 πΆπ£ π 7 π3π2 πΆπ£ π = π4π1 πΆπ£ π 8 But the point D(P3,V3) at T2 and point A(P4,V4) at T1 are lie on same adiabatic curve AD. Divide equation (7) by (8)- π1 π4 = π2 π3 . 9 From equation (9) and (6), we have- Wm = = ππ π1 ln π1 π4 - ππ π2 ln π1 π4 Wm = (q1 β q2) = nR (T1 - T2) ππ π½π π½π 10
- 53. Efficiency of Carnot heat engine: Ratio of the total work done by the working substance and total heat absorbed from the source. It is denoted by the latter Ξ· or Ξ΅. Ξ΅ = ππππ₯ π1 11 = π1β π2 π1 = 1 - π2 π1 12 Also from equation (10), (1a) and (11), Ξ΅ = nR (T1 β T2 ) ln π1 π4 ππ π1 ln π1 π4 = T1 β T2 T1 = 1 - T2 T1 13 efficiency of Carnot heat engine depends on heat absorbed or given out to sink Ξ΅ depends on the temperature of source and sink but not depends on the nature and amount of the working substance
- 54. Thermodynamic efficiency ο± For reversible and cyclic process of the system, if it absorb heat q1 at T1, then it undergoes a temperature change (T1 - T2) and the maximum work done is equal to the heat absorb q1 at T1 multiplied by the ratio (T1 - T2)/ T1. Ξ΅ = ππππ₯ π1 = T1 β T2 T1 π πππ₯ = T1 β T2 T1 π₯ π1 ο± The some part of heat rejected at temperature T2 such that T1>T2. ο± The magnitude of the work done is given by the area of the P-V diagram of Carnot cycle. ο± For 100% thermodynamic efficiency, T2 = 0 i.e. temperature of the sink is zero K. To maintain such temperature of the sink or surrounding is practically impossible.
- 55. Carnot Theorem/Rule Developed by Nicolas LΓ©onard Sadi Carnot in the year 1824, with the principle that there are limits on maximum efficiency for any given heat engine. Carnotβs theorem states that: ο Heat engines working between two heat reservoirs are less efficient than the Carnot heat engine (reversible engine) that is operating between the same reservoirs. ο Efficiency of all reversible engines working between the same two temperatures (same source and the sink) is same whatever the working substance. ο Maximum efficiency is given as: ππππ₯ = ππΆπππππ‘ = ππΆ ππ» ππΆ is absolute temperature of the cold reservoir ππ» is absolute temperature of the hot reservoir
- 56. Consider two heat engines R (reversible engine) and I (irreversible engine) working between the same source (T1) and the same sink (T2), where T1>T2. Reversible engine R takes heat Q1 from the source (T1), perform work W and rejects some heat Q2 = Q1 βW to the same sink (T2). The efficiency of the reversible engine R is: ππ = π π1 Suppose irreversible engine I takes heat π1 β² from the source (T1), perform work W and rejects some heat π2 β² = π1 β² β π to the same sink (T2). ππΌ = π π1 β² The efficiency of the irreversible engine I is: Suppose, the irreversible engine I is more efficient than the reversible engine R. ππΌ > ππ βΉ π π1 β² > π π1 β π1 > π1 β² β π1 β π1 β² ππ πππ ππ‘ππ£π ππ’πππ‘ππ‘π¦ Where, W work done is same.
- 57. These two engines are coupled together so that the engine R works in opposite direction i.e. the engine R works as a refrigerator. The engine I absorbs heat π1 β² from the source (T1), perform work W and rejects some heat π2 β² = π1 β² β π to the same sink (T2). The engine R takes heat Q2 from the same sink (T2), perform work W on the engine R and Q1 = Q2 + W heat is rejected to the source (T1). Work done on the gas by the engine R is actually received from the work done by the gas on the engine I. Heat lost by the sink is: π2 β π2 β² = π1 β π β π1 β² β π β π1 β π1 β² ππ π πππ ππ‘ππ£π ππ’πππ‘ππ‘π¦ i.e. external work done on the system is zero. both the engines R and I work as a self-acting machine The coupled engines transfers heat continuously from a body at lower temperature to the body at higher temperature. contrary to the second law of thermodynamics. i.e. our assumption ππΌ > ππ is wrong. i.e. no engine will be more efficient than a perfectly reversible engine working between the same temperatures (same source and same sink)
- 60. Second law of thermodynamic The first law of thermodynamic state that, when one form of energy is converted into another, the total energy of the system is conserved. It does not indicate any other restriction on this process and many of the process has a natural direction. This direction can be explained by using a second law of thermodynamics. e.g. Suppose gas in expand into a vacuum but although it does not violate first law of thermodynamics; the reverse does not occur, etc. Second law of thermodynamic tell us that whether the reaction take places in forward or in backward direction or direction of flow energy. The quantity tells us that whether a chemical change or physical process is spontaneous or not in an isolated system in terms of a new thermodynamic function called as entropy. Entropy is a state function. Thermodynamic does not explain the rate of reaction/change to approach the equilibrium state, but it explains at equilibrium state. e.g. i) Gas is expand into vaccum, ii) Heat is always transfer from hot end to cold end of the rod, iii) In presence of catalyst, molecular hydrogen is react with molecular oxygen to form water.
- 61. Different Statements of Second Law of Thermodynamics: Definition by Clausius: There is no thermodynamic transformation whose sole effect is to deliver heat from a reservoir of lower temperature to a reservoir of higher temperature Heat does not flow upwards i.e. lower to higher temperature spontaneously. In an isolated system, the entropy never decreases. Definition by Kelvin: There is no thermodynamic transformation whose sole effect is to extract heat from a reservoir and convert it entirely to work. No heat engine is constructed having unit efficiency.
- 63. Entropy (S) Second law of thermodynamic can be expressed mathematically by a new thermodynamic functions S called as entropy of the system. Entropy of the system is a state function ΞS = S2 - S1 Where, S2 and S1 are entropies of final and initial states of the system respectively. dqrev/T is the differential of the state function. Clausius named this state function is entropy dS. For infinitesimal change: ππ = πππππ£ π For finite change in state: βπ = πππππ£ π = ππππ£ π Where dqrev is the infinitesimal quantity of heat absorbed under reversible conditions at temperature T. Also qrev is the heat absorbed at any temperature T for any isothermal reversible process. ππππ£ is the positive (heat is absorbed)- ΞS is positive (entropy of the system increases) ππππ£ is the negative (heat is evolved)- ΞS is negative (entropy of the system decreases) Endothermic Exothermic
- 64. Derivation of entropy from Carnot cycle The heat q1 is taken by the working substance from source at temperature T1 and heat q2 is given out by the working substance at lower temperature T2. Efficiency of Carnot engine Ξ΅ = πΎπππ ππ π1β π2 π1 = T1 β T2 T1 1 - π2 π1 = 1 - T2 T1 π2 π1 = T2 T1 or π2 T2 = π1 T1 q1 has positive value and q2 has a negative value. β π2 T2 = π1 T1 or π1 T1 + π2 T2 = 0 In general: π π = 0 For a complete reversible cycle represented by the close curve ABA For reversible cycle ABA: π π = 0 Since the cycle is performed in two steps; via from A to B and then back from B to A, we have: ππ π = π΄ π΅ ππ π + π΅ π΄ ππ π = 0 ππ π = π΄ π΅ ππ π = β π΅ π΄ ππ π Both these integrate shows that π π π» is independent on the path but it depends on the state of the system. This function ππ π is called as entropy and is state function.
- 65. Second law of thermodynamic i) Natural process are irreversible and spontaneous, it is accompanied by increase in entropy of the universe. Universe means the system and its surrounding. ΞSuniv. = ΞSsystem + ΞSsarr. > 0. But for reversible process, entropy of the system remains constant. ΞSuniv. = 0. ii) Heat can not be converted to work without leaving permanent change either in systems involved or their surrounding. iii) It is impossible to take heat from a hot reservoir and convert it completely into work by cyclic process without transforming a part of heat to a cooler reservoir i.e. it impossible to construct an engine having unit efficiency. iv) It is impossible for a cyclic process to transfer heat from a body at a lower temperature to a body of higher temperature in absence of any agency.
- 66. Here are 5 different ways to state the second law of thermodynamic 1. For any spontaneous process the entropy of the universe increases. 2. It is impossible for heat to spontaneously flow from a cold object to a hot object. 3. No steam engine can be more efficient than a reversible steam engine (Carnot theorem). 4. It is impossible to build a perfectly efficient steam engine. 5. It is impossible to build a perpetual motion machine of the second kind.
- 67. Entropy change in Physical transformations Change in entropy occur not only variations of temperature, pressure and volume of the system but also physical transformation such as change of state from solid to liquid (melting), liquid to vapour (boiling) and solid to vapour (sublimation) At constant temperature, two phases are in equilibrium during phase transformation by an absorbing or evolving heat. βπ = ππ π = β π» π For melting For one mole of substance, it absorb a heat is called as latent/molar heat of fusion at constant temperature T is called as melting point. The change in entropy is: βππ= β π»π ππ For boiling It absorb a heat is called as latent/molar heat of vaporization at constant temperature T is called as boiling point. The change in entropy is: βππ£= β π»π£ ππ One mole of solid is change to another allotropic form at constant allotropic transition temperature. The change in entropy is: For allotropic transition βππ‘= β π»π‘ ππ‘
- 68. β’ According to the physical significance of entropy- In Carnot cycle, only some part of heat is converted into work and remaining part of heat is given to sink. The part of heat which is not available to perform work is a measure of entropy change accompanying the process. Hence the fraction of energy unavailable to perform the work is T.ΞS. S = q/T = βH/T Fraction available to perform work = (ΞH) - T.ΞS.
- 69. Physical significance of entropy (b) i.e. melting at constant temperature Tf, the heat absorbed by the solid particles to go to liquid state is ΞHf. The addition of heat to the system introduces more randomness or disorder in the system e.g. when solid melts, the ordered arrangement of the constituent particles is destroyed and particles acquired greater freedom of movement. Change in entropy is: βππ= β π»π ππ ΞHf is positive and hence βππ is also positive i.e. Ssolid < Sliquid Similarly for boiling of liquid, the constituent particles of gas have more degree of freedom and more disorder system is formed. entropy is taken as a measure of disorder of the system
- 70. (c) Entropy of the system is taken as a measure of mixtupness of the system When organized from of energy such as electric, mechanical or chemical is converted into heat, the randomness of the system increases as the constituent particles of the system acquired greater degree of freedom of movement. It increases the disorder in the system, increase its mixtupness. (d) Entropy of the system is also used to measured thermodynamic probability of the system. S = k lnW (put by Plank in 1912) Where, S is entropy, W is thermodynamic probability, k is Boltzmann constant.
- 71. Entropy as criteria of Spontaneity & Equilibrium (a) For irreversible process: Consider a system in contact with a reservoir at constant temperature T, assume that in the system an infinitesimal irreversible process (spontaneous) occurs and work done is of P-V type. The quantity of heat dq is exchanged between the system and reservoir. Therefore, entropy change of system is dS and that of reservoir is β dq/T. dS > dq/T TdS > dq dq β TdS < 0 (1) According to the first law of thermodynamics - dq = dE + PdV (2) From equation (1) and (2)- dE + PdV β TdS < 0 (3) Condition of entropy change: Consider the system having constant volume and internal energy i.e. dE = dV = 0, therefore equation (3) becomes: -(TdS)E,V < 0 (TdS)E,V > 0 or (dS)E,V > 0 (4) And for finite change - (ΞS)E,V > 0 Reversible change: change < , > replaced by = sign in above.
- 72. Entropy Change in Ideal Gases The change in entropy of an isolated system is zero or greater than zero. πππ = πππ π’π. + πππππ ππ. β₯ 0 dSi is change in entropy of isolated system dSsub is change in entropy of working substance dSreser is change in entropy of heat reservoir The heat is supplied by the heat reservoir to working substance at constant temperature T. πππππ ππ. = ππ π From above equation: πππ π’π. + ππ π β₯ 0 According to the first law of thermodynamics dq = dE + dw But if system does work is only P-V type, then dq = dE + pdV And if the system does the work other than P-V type then: dq = dE + pdV + dwβ Put dq in above equation: dSsub β (dE + pdV + dwβ)/T β₯ 0 Multiplying both side by T, TdSsub β (dE + pdV + dwβ) β₯ 0 The inequality is applied to irreversible processes, where only P-V work is done and dWβ= 0 and p = P, TdSsub β (dE + PdV) > 0 (for irreversible process)
- 73. For reversible processes, dwβ = dWβ and p = P, TdSsub β (dE + PdV + dWβ) = 0 But when dWβ = 0, TdSsub β (dE + PdV) = 0 For reversible isothermal process dE = 0, TdSsub β PdV = 0 dSsub = π·ππ π For n mole of ideal gas: PV = nRT P = ππ π π or Therefore, dS is dSsub = ππ π ππ Integrate with the limits of entropy S1 and S2 at the volume V1 and V2: π1 π2 ππ = ππ π1 π2 ππ π π2 β π1 = ππ ln π2 π1 ΞS = ππ ln π2 π1 Expansion process ΞS = π. πππ ππ log π2 π1 Entropy change for the reversible isothermal compression process is: ΞS = 2.303 ππ log π1 π2
- 74. *** Free Energy and Equilibrium *** β’ How much quantity of heat is used to performed work done is determined by mew thermodynamic state function is called as free energy. The heat energy is supplied in the form of internal energy or enthalpy. [Heat energy (E or H)] = (Heat available to perform work done) + (Heat unavailable to perform work done) If heat energy is supplied in the form of internal energy (E), the part of internal energy available to perform work is called Helmholtz free energy. It is denoted by the latter A. The internal energy unavailable to perform the work done is TS, S-is entropy at temperature T. [Heat energy (E)] = (E available to perform work done) + (E unavailable to perform work done) E = A + TS A = E - TS (1)
- 75. If heat energy is supplied in the form of enthalpy (H), the part of enthalpy available to perform work is called Gibbs free energy. It is denoted by the latter G or F. The enthalpy unavailable to perform the work done is TS, S-is entropy at temperature T. [Heat energy (H)] = (H available to perform work done) + (H unavailable to perform work done) H = G + TS G = H - TS (2)
- 76. Helmholtz free energy Helmholtz free energy of any system A is defined as - A = E - TS Where, A, E, S and T are state functions. The change in A during any process is given as- ΞA = A2 - A1 = (E2 β T2S2) β (E1 β T1S1) = (E2 - E1) β (T2S2 β T1S1) = ΞE β ΞTS (3) Equation (3) is the general definition of ΞA. For isothermal process T2 = T1, then equation (3) becomes- ΞA = ΞE β TΞS (4) Eq. (4) explain physical interpretation (significance) of ΞA, under isothermal conditions β TΞS = qrev (according to the definition of change in entropy). ΞA = ΞE β qrev. (5) According to the first law of thermodynamics for reversible and isothermal process- qrev = ΞE + Wmax or -Wmax = ΞE - qrev (a) From equation (5) and (a)- ΞA = -Wmax (6) The equation (6) indicates that, at constant temperature, the maximum work done by the system is due to expense of (decrease in) Helmholtz free energy. Therefore, A is called as Work function of a system.
- 77. Relationship between G and A Consider equation (3) is- ΞG = ΞH β TΞS But H is also state function- ΞH = ΞE + PΞV (at constant P) Therefore, ΞG = ΞE + PΞV β TΞS = (ΞE β TΞS) + PΞV (ΞA = ΞE β TΞS) ΞG = ΞA + PΞV (4) In general- G = A + PV (5) The equation (4) and (5) shows the relationship between G and A.
- 78. A and G as criteria for Thermodynamic Equilibrium and Spontaneity Condition of Helmoholtz free energy change If system is not isolated system then its entropy can be changed. If volume of the system remains constant for irreversible process i.e. dV = 0 then, dE β TdS < 0 At constant V and T, for infinite small change: (βE β TβS)T,V < 0 β(E β TS)T,V < 0 Or According to the definition of A, A = E β TS β(A)T,V < 0 then And for finite change: (ΞA)T,V < 0 Thus, for any irreversible or spontaneous process in a system at constant volume and temperature, the Helmoholtz free energy of the system decreases therefore stable state is obtained at the lowest Helmoholtz free energy. Helmoholtz free energy is state function, therefore at equilibrium state (ΞA)T,V = 0 dE + PdV β TdS < 0
- 79. Gibbs free energy is state function, therefore at equilibrium state (ΞG)T,P = 0 Condition of Gibbs free energy change If system is not isolated system then its entropy can be changed. If pressure and temperature of the system remains constant for irreversible process i.e. dP = dT = 0 dE + PdV β TdS < 0 At constant P and T, for infinite small change: (βE + PβV β TβS)T,P < 0 Or β(E + PVβ TS)T,P < 0 Or β(H β TS)T,P < 0 According to the definition of G, G = H β TS β(G)T,P < 0 And for finite change: (ΞG)T,P < 0 Thus, for any irreversible or spontaneous process in a system at constant pressure and temperature, the Gibbs free energy of the system decreases therefore stable state is obtained at the lowest Gibbs free energy.
- 80. Variation of A with T and V: Differentiate it completely as - dA = dE β TdS - SdT (7) According to the definition of entropy - dqrev = TdS Therefore equation (7) becomes- dA = dE - dqrev - SdT (8) According to the first law of thermodynamics- dqrev = dE + PdV (for reversible process) Or -PdV = dE - dqrev Therefore equation (8) becomes - dA = - PdV - SdT (9) Equation (9) indicates that A is most conveniently expressed in terms of a T and V as the independent variables, we have- A = f (T,V) Differentiate it completely- dA = (Ξ΄A/Ξ΄T)v dT + (Ξ΄A/Ξ΄V)T dV (10) Comparing equation (9) and (10) we have- (Ξ΄A/Ξ΄V)T = -P (11) (Ξ΄A/Ξ΄T)v = -S (12)
- 81. β’ An alternative equation for the variation of A with T can be obtained as follows- β’ Differentiate A/T with respect to T at constant V gives - β’ [Ξ΄(A/T)/Ξ΄T]v = [T(Ξ΄A/Ξ΄T)v β A]/T2 β’ = [T(-S) β A]/T2 β’ = - [A + TS]/T2 β’ = - E/T2 (13) β’ Equation (9) shows that the dependence of A for a pure substance on both T and V, these can be shown by (12) and (13) for T and (11) for V.
- 82. Variation of G with P and T According to the definition of G [i.e. from equation (1)]- G = H - TS Differentiate it completely as- dG = dH - TdS - SdT (7) According to the definition of entropy and first law of thermodynamics- dqr = TdS = dE + PdV (for reversible process) (8) According to the definition of enthalpy- H = E + PV Differentiate it completely- dH = dE + PdV + VdP (9) Therefore equation (8) and (9) dH = VdP + TdS (10) From equation (7) and (10)- dG = VdP + TdS -TdS -SdT dG = VdP - SdT (11) Equation (11) indicates that G is function of a T and P as the independent variables, we have- G = f (T,P)
- 83. G = f (T,P) Differentiate it completely- dG = (Ξ΄G/Ξ΄T)P dT + (Ξ΄G/Ξ΄P)T dP (12) Comparing equation (11) and (12) we have- (Ξ΄G/Ξ΄P)T = V (Ξ΄G/Ξ΄T)P = -S (13) An alternative equation for the variation of G with T can be obtained as follows- Differentiate G/T with respect to T at constant P gives- [Ξ΄(G/T)/Ξ΄T]P = [T(Ξ΄G/Ξ΄T)P β G]/T2 = [T(-S) β G]/T2 = - [G + TS]/T2 = -H/T2 (14) Equation (11) shows that the dependence of G for a pure substance on both T and P, these can be shown by (14) and (13) for T.
- 84. Advantage of G/A over Entropy change The first law of thermodynamics /energy conservation, but one can't comment on the nature of a process (spontaneous or non-spontaneous). Hence knowing only the quantity of energy change is never sufficient. The second law is defined in the terms of both entropy and Gibbs free energy. For a process to be spontaneous: β π π‘ππ‘ππ > 0 πππ βπΊ < 0 Hence both entropy and Gibbs free energy changes can help you determine the spontaneity of a process Entropy change for a reversible process: βπ = ππππ£ π Criteria for spontaneity is the total entropy: β π π‘ππ‘ππ > 0 and β π π‘ππ‘ππ = β π π π¦π π‘ππ + β π π π’ππππ’πππππ It is extremely difficult task to determine the entropy change in surrounding therefore converting it to Gibbs free energy. β π π‘ππ‘ππ = ππ π¦π π‘ππ π + ππ π’ππππ’πππππ π & ππ π’ππππ’πππππ = βπ»π π’ππππ’πππππ = ββπ»π π¦π π‘ππ Hence, β π π‘ππ‘ππ = β π π π¦π π‘ππ β βπ»π π¦π π‘ππ π
- 85. Multiplying by T and rearranging, π β π π‘ππ‘ππ = π β π π π¦π π‘ππ β βπ»π π¦π π‘ππ βπΊ = β π β π π‘ππ‘ππ = β π β π π π¦π π‘ππ + βπ»π π¦π π‘ππ ΞS(total) must be greater than zero, ΞG must be less than zero. Hence, Gibbs free energy reduces the tedious work of determining entropy change in surrounding and it's value can determined by knowing the state of the system only. Gibbs free energy is more advantageous than entropy change.
- 86. Chemical equilibrium A + B β C + D Based on the extent to which the reactions proceed to reach the state of chemical equilibrium: (i) The reactions that proceed nearly to completion and only negligible concentrations of the reactants are left. In some cases, it may not be even possible to detect these experimentally. (ii) The reactions in which only small amounts of products are formed and most of the reactants remain unchanged at equilibrium stage. (iii) The reactions in which the concentrations of the reactants and products are comparable, when the system is in equilibrium.
- 87. A + B β C + D
- 88. There are number of important questions about the composition of equilibrium mixtures: What is the relationship between the concentrations of reactants and products in an equilibrium mixture? How can we determine equilibrium concentrations from initial concentrations? What factors can be exploited to alter the composition of an equilibrium mixture? Particular is important when choosing conditions for synthesis of industrial chemicals such as H2, NH3, CaO etc.
- 89. Equilibrium constant Law of mass action The rate of a chemical reaction at any instant is proportional to the molar concentration of the reacting substance at that instant Consider the simplest reaction β A β product. If CA is the concentration of the reactant at time t, then- Rate = ο‘ CA The proportionality constant in the above rate equations is called rate constant or velocity constant or specific rate constant
- 90. Reversible reaction k k f b A B Depending on the physical state of the reactants and products, two physical constants for reversible reaction is defined as KP and KC. At gaseous state, the equilibrium constant KP is in terms of partial pressures of reactants and products For other states or liquid/solution state, it is denoted by KC which is in terms of partial concentrations.
- 91. aA + bB lL + mM A & B are reactants (behaves ideally) L & M are products (behaves ideally) a & b and c & d are number of moles of reactants and products respectively. general reaction are the molar concentrations of A, B, C and D respectively. Characteristics of Kc: β’When concentrations of the reactants and products have attained constant value at equilibrium state. β’ Value of equilibrium constant is independent of initial concentrations of the reactants and products. β’ Equilibrium constant is temperature dependent having one unique value for a particular reaction represented by a balanced equation at a given temperature. β’ The equilibrium constant for the reverse reaction is equal to the inverse of the equilibrium constant for the forward reaction. KC
- 92. Because gas pressures are easily measured, equilibrium equations for gas-phase reactions are often written using partial pressures rather than molar concentrations. For the gaseous state, the partial pressure is also measure the activity of the component, KP is - are the molar concentrations of A, B, C and D respectively. KP aA + bB lL + mM A & B are reactants (behaves ideally) L & M are products (behaves ideally) a & b and c & d are number of moles of reactants and products respectively.
- 93. Relationship between KP and KC For n mole of ideal gas - pV = nRT p = = But n/V = C, therefore, p = C R T. Equations for KP and KP are - aA + bB lL + mM A & B are reactants (behaves ideally) L & M are products (behaves ideally) a & b and c & d are number of moles of reactants and products respectively. But (l + m) - (a + b) = βn, therefore, K = p K C (RT) n
- 94. Le Chatelierβs Principle Equilibrium constant, Kc is independent of initial concentrations. But, if a system at equilibrium is subjected to a change in the concentration of one or more of the reacting substances, change in temperature or pressure of the system or catalyst can affect equilibrium can be explain by Le Chatelierβs principle. A change in any of the factors that determine the equilibrium conditions of a system will cause the system to change in such a manner so as to reduce or to counteract the effect of the change. Effect of Concentration Change Effect of Pressure Change Effect of Inert Gas Addition Effect of Temperature Change Effect of a Catalyst
- 95. Effect of Concentration Change When the concentration of any of the reactants or products in a reaction at equilibrium is changed, the composition of the equilibrium mixture changes so as to minimize the effect of concentration changes ) π»2 π + πΌ2 π β 2 π»πΌ (π πΉπ3+ ππ + ππΆπβ ππ β πΉπ ππΆπ 2+ ππ yellow colourless deep red πΎπ = πΉπ ππΆπ 2+ ππ πΉπ3+ ππ ππΆπβ ππ The intensity of the red colour becomes constant on attaining equilibrium Oxalic acid (H2C2O4), reacts with Fe3+ ions to form the stable complex ion [Fe(C2O4)3]3β, thus decreasing the concentration of free Fe3+ (aq); the concentration of [Fe(SCN)]2+ decreases, the intensity of red colour decreases. Similar effect was found by the addition of aq. HgCl2 because Hg2+ reacts with SCNβ ions to form stable complex ion [Hg(SCN)4]2β
- 96. Effect of Pressure Change Affect in case of a gaseous reaction where the total number of moles of gaseous reactants and total number of moles of gaseous products are different. The effect of pressure changes on solids and liquids can be ignored because the volume (and concentration) of a solution/liquid is nearly independent of pressure πͺπΆ π + π π―π β πͺπ―π π + π―ππΆ π 4 mol of gaseous reactants (CO + 3H2) become 2 mol of gaseous products (CH4 + H2O) As, total pressure will be doubled (according to p.V = constant), partial pressure and therefore, concentration of reactants and products have changed and the mixture is no longer at equilibrium. The equilibrium now shifts in the forward direction. Effect of Inert Gas Addition If the volume is kept constant and an inert gas such as argon is added which does not take part in the reaction, the equilibrium remains undisturbed because it does not change the partial pressures or the molar concentrations of the substance involved in the reaction
- 97. Effect of Temperature Change when a change in temperature occurs, the value of equilibrium constant, Kc is changed. In general, the temperature dependence of the equilibrium constant depends on the sign of βH or βG for the reaction. ο± The equilibrium constant for an exothermic reaction (negative βH) decreases as the temperature increases. ο± The equilibrium constant for an endothermic reaction (positive βH) increases as the temperature increases. ) π π―π π + π΅π π β π π΅π―π (π βH= β 92.38 kJ molβ1. exothermic process raising the temperature shifts the equilibrium to left and decreases the equilibrium concentration of ammonia.
- 98. The Reaction isotherm (Vanβt Hoffβs Isotherm) Vanβt Hoffβs isotherm gives the net work done that can be obtained from gaseous reactants at constant temperature, when both reactants and products are at suitable orbitary pressure. Consider a general reaction- If aA, aB, aC and aD are activities of reactants A, B and products C, D respectively. The free energies of each of these substances per mole at T is- GA = Go A + RT lnaA (1) GB = Go B + RT lnaB (2) GC = Go C + RT lnaC (3) GD = Go D + RT lnaD (4) Where, Go A, Go B, Go C and Go D are the free energies at unit activity of the A, B, C and D respectively or are the standard free energies of A, B, C and D respectively. aA + bB + ............ cC + dD + .................. A quantitative relation of the free energy change for the chemical reaction has been developed which is known as Reaction isotherm or Vanβt Hoffβs isotherm.
- 99. Therefore the free energy change of the chemical reaction - ΞG = Ξ£Gp β Ξ£GR = [cGC + dGD + β¦β¦.] β [aGA +bGB + β¦β¦..] = [cGoC + RT lnaC c + dGoD + RT lnaD d + β¦β¦.] β [aGoA + RT lnaA a + bGo B + RT lnaB b + β¦β¦..] = [(cGoC + dGoD + β¦β¦) β (aGoA + bGoB +β¦β¦)] + RT[(lnaC c + lnaD d + β¦β¦.) β (lnaA a + lnaB b + β¦β¦..)] ΞG = ΞGo + RT ln{(aC c.aD dβ¦β¦.)/(aA a .aB bβ¦β¦..)} (5) The equation (5) is called as the Vanβt Hoffβs isotherm or reaction isotherm. When activities of all reactants and products are equal to one then ΞG = ΞGo . At equilibrium step of the reaction - ΞG = 0 0 = ΞGo + RT ln{(acC x adDβ¦β¦.)/(aaA x abBβ¦β¦..)} At equilibrium, according to the law of mass action, Ka = (acC adDβ¦β¦.)/(aaAabBβ¦β¦..) Therefore, 0 = ΞGo + RT ln Ka Or ΞGo = - RT ln Ka (6) Ka = e -ΞGo/RT (7) Form equation (5) and (6)- ΞG = RT ln{(acC adDβ¦β¦.)/(aaAabBβ¦β¦..)} - RT ln Ka = RT ln Qa - RT ln Kaa where Qa = {(acC adDβ¦β¦.)/(aaAabBβ¦β¦..)} = RT ln (Qa/Ka) (8)
- 100. For gases activities are proportional to the partial pressures of the components of reaction mixture hence the activities of the equation (5) can be replaced by the partial pressures, therefore- ΞG = ΞGo + RT ln{(PC c.PD dβ¦β¦.)/(PA a.PB bβ¦β¦..)} (9) = RT ln Qp - RT ln Kp (10) Where Kp is the equilibrium constant and Qp = (Pc C.Pd Dβ¦β¦.)/(Pa A.Pb Bβ¦β¦..) At equilibrium state, ΞG = ΞGo and Qp = 1. ΞGo = - RT ln Kp = -W or Kp = e -ΞGo/RT (11) i.e. net work done of the reaction is equal to the decrease in free energy of the system and it is calculated by using expression - RT ln Kp or 2.303RT log Kp. It will be observed that, ΞG is positive when Kp is less than unity. If ΞG is negative when Kp is greater than unity and is zero when Kp = 0 or 1.
- 101. *** Vanβt Hoff Isochore *** The Vanβt Hoff isochore is obtained by comparing the Vanβt Hoff isotherm with Gibbs - Helmeholtz equation. The Gibbs-Helmeholtz equation is ΞG = ΞH + T[d(ΞG)/dT]p Or -ΞH = T[d(ΞG)/dT]p - ΞG Dividing both side by T2 gives:- -ΞH/T2 = {T[d(ΞG)/dT]p - ΞG}/T2 The right hand side of the above equation is obtained by differentiating ΞG/T w.r.t. T at constant P- [d(ΞG/T)/dT]p = {T[d(ΞG)/dT]p - ΞG}/ T2 -ΞH/T2 = [d(ΞG/T)/dT]p (12) β’ According to Vanβt Hoff isotherm- ΞG = -RT ln Kp (11) β’ Dividing both side by T and differentiating it w.r.t. T at constant P- β’ [d(ΞG/T)/dT]p = -R d(lnKp)/dT (13) β’ Comparing equation (13) and (12), we have- β’ ΞH/T2 = R d(lnKp)/dT β’ Or (ΞH/R).dT/T2 = d(lnKp) (14) β’ The above equation is known as Vanβt Hoff isochore. If ΞH remains same over the range of temperature, we have on integration - β’ lnKp = (ΞH/R)β«dT/T2 β«dx/xn = 1/(-n+1).1/xn-1 β’ = -ΞH/RT + constant of integration. β’ Appling the limits T1 and T2 at the equilibrium constants Kp1 and Kp2 respectively, we have- β’ lnKp2 - lnKp1 = -(ΞH/R)[1/T2 - 1/T1] β’ ln[Kp2/Kp1] = (ΞH/R)[1/T1 - 1/T2] β’ log[Kp2/Kp1] = (ΞH/2.303R)[(T2 β T1)/T1T2] (15) β’ By using this equation, equilibrium constant at any temperature or heat of reaction is calculated.
- 102. Vapour pressure of Liquid Clapeyron equation For any pure substance in a single phase such as liquid or gaseous, are in contact with each other then any variation in free energy is given by the equation. dG = VdP β SdT (1) If these two phases are in equilibrium to each other, then dG = 0 at constant pressure and temperature i.e. dP = dT = 0 i.e. these phases are in equilibrium with other when the pressure and temperature are constant and uniform throughout the phase. βA useful thermodynamic equation is applicable to a system consisting of two phases of same substance in equilibrium is called as Clapeyron equation.β Consider the transition of a pure substance from one phase into another phase e.g.- 1. Solid convert to liquid- at melting point of solid- melting or fusion. 2. Liquid convert to vapour- at boiling point of liquid- boiling or vaporization. 3. Solid convert to vapour- at sublimation point of solid- sublimation. 4. Allotropic transitions at the transition temperature of the two allotropic forms. e.g. S(rhombic) is in equilibrium with S(monoclinic). All above changes are represented by the reaction- For which ΞG is given as- ΞG = G2 βG1 (2) Where, G2 and G1 are the molar free energies of the substances in final and initial states respectively. At equilibrium state ΞG = 0, at constant P and T i.e. G1 = G2. All such transformations will be in equilibrium at constant pressure and at constant temperature, when molar free energies of the substances are identical in both phases. A1 A2
- 103. Clapeyron equation ΞG = G2 βG1 = 0. i.e. G1 = G2 Or dG1 = dG2 (3) The variation of free energies for pure substances with respect to P and T in single phase is given by the equation- dG1 = V1dP β S1dT (4) dG2 = V2dP β S2dT (5) Where, order to maintain equilibrium, the temperature is changed by the amount dT and that of pressure is dP. From equation (3), (4) and (5)- V2dP β S2dT = V1dP β S1dT (V2 β V1) dP = (S2 β S1) dT dP/dT = (S2 β S1)/(V2 β V1) = ΞS/ΞV (6) Where, ΞS is change in entropy and ΞV is change in volume during transformation. But- ΞG = ΞH β TΞS, But at equilibrium, ΞG = 0. Or ΞH = TΞS or ΞS = ΞH/T (7) From equation (6) and (7)- dP/dT = ΞH/T.ΞV (8) Where, ΞH is the change in enthalpy for reversible transformation occurring at temperature T. this equation is called as Clapeyron equation. The Clapeyron equation gives relation between the temperature and pressure of the system containing two phases of a pure substance which are in equilibrium with each others. This equation also shows that dP/dT is directly proportional to the enthalpy of the transition and inversely proportional to temperature and the volume change accompanying during the transition i.e. ΞH and ΞV are the functions of temperature and or pressure. The equation (8) can be modified as- (P2 β P1)/(T2 β T1) = ΞH/T.ΞV (9) Where T is taken as average of T2 and T1 or equation (8) can be integrated with the proper limits of T and P by assuming that ΞH and ΞV are constant. P2 T2 β«dP = ΞH/ΞV β« dT/T P1 T1 (P2 β P1) = (ΞH/ΞV) ln T2/T1. (P2 β P1) = (2.303ΞH/ΞV) ln T2/T1. (10)
- 104. Vapour pressure of Liquid The variation of vapour pressure with temperature can be expressed thermodynamically by means of Clausius-Clapeyron equation. Let us consider a system- For the transition of liquid to vapour, P is the vapour pressure at given temperature T; ΞHv is the heat of vaporization of liquid. The volume of given liquid is Vl and that of vapour is Vg. Therefore, the Clepeyron equation can be written as- dP/dT = [ΞHv /T(Vg β Vl)] (1) But molar volume of the substance in vapour phase is very large as compaired to volume of same liquid in liquid state. (Vg β Vl) β Vg. (18 ml water liquid = 22400 ml water vapour) Therefore, the Clepeyron equation becomes- dP/dT = ΞHv/TVg. (2) If we assume that the vapour behaves ideally then Vg per mole of substance can be calculated as- Vg = RT/P (3) Substituting (3) in equation (2) as- dP/dT = PΞHv/RT2. (4) dP/P = (ΞHv/R). dT/T2 (5) d(lnP) = (ΞHv/R). dT/T2 (6) The equation (6) is known as the Clausius-Clapeyron equation. The heat of vaporization is a function of temperature. Assume that ΞHv will be independent on the temperature (constant over the range of temperature and pressure). Liquid vapour
- 105. Vapour pressure of Liquid Then equation (6) can be integrated- (a) Integrated without limits of temperature and pressure:- β«d(lnP) = (ΞHv/R) β«dT/T2 + C (C is constant of integration) (lnP) = (ΞHv/R) . (-1/T) + C (logP) = (-ΞHv/2.303RT) + Cβ (7) The equation (7) shows that logarithm of the vapour pressure should be a function of the reciprocal of the absolute temperature T. It is also a equation of straight line of the type, y = mx+c. Plot a graph of logP against 1/T is a straight line having slope = m = (-ΞHv/2.303R) and Y-intercept c = Cβ. From the slope of the graph, heat of vaporization of the various liquids can be calculated as- m = (-ΞHv/2.303R) (8) ΞHv = (-2.303R . m) = -4.576 . m cal/mol. (b) Integration with limits:- Integrate equation (6) with the limits of pressure P1 and P2 corresponding to the temperature T1 and T2, then- P2 T2 β«d(lnP) = (ΞHv/R) β«dT/T2 P1 T1 P2 T2 [lnP] = (ΞHv/R) [-1/T] P1 T1 ln(P2/P1) = (ΞHv/R) [(T2 β T1)/T1T2] (9) log(P2/P1) = (ΞHv/2.303R) [(T2 β T1)/T1T2] (10) The equation (10) can be used to calculated ΞHv from the values of the vapour pressure at any two temperatures or when ΞHv is known, P at some desired temperature can be calculated from a single available vapour pressure at a given temperature.
- 106. Thank you