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The process in which thermal energy is converted into mechanical
energy and vice-versa is called Thermodynamics.
Thermochemical Reactions The reactions in which material change is accompanied by heat energy change is called a thermochemical reaction. There are two types of thermochemical reactions: i) Endothermic Reactions: Heat is absorbed in endothermic reactions. The enthalpy value (ΔH) is positive for endothermic reactions. For example: CaCO3 CaO + CO2 ΔH=+ve ii) Exothermic Reaction Heat is released in exothermic reactions. The enthalpy value (ΔH) is negative for endothermic reactions. All the combustion reactions are exothermic in nature. For example: C + O2 CO2 ΔH=-ve KJ/mol Thermodynamic Terms System: Any real or imaginary portion of the universe which is under examination is called a system. System may be homogenous (single state) or heterogeneous (more than one state). Types of System: There are 3 types of system. 1. Open System: Both energy and mass can be transferred. 2. Closed System: Only energy can be transferred. 3. Isolated System: Neither energy nor mass can be transferred. Surrounding: The part of Universe around the system. Boundary: The border between system and surrounding. State: P, V, T, E & H are called state of a system. Macroscopic Properties The properties of a system in bulk which are easily measurable are known as the macroscopic properties. e.g: Pressure, Temperature, Volume etc. Intensive Properties: Independent of amount. example: Density, Pressure, Temperature, viscosity, surface tension, refractive index, melting point, boiling point etc. Extensive Properties: dependent of amount. Example: Mass, Volume, Mole, Enthalpy, Entropy (disorderness of system), Internal energy etc. First Law of Thermodynamics (Law of conservation of Energy) Helmholtz - 1847 Statement: “Energy can neither be created nor destroyed but it can be changed from one form to another.” “Total energy of system and surrounding always remain constant.” If ‘q’ be the heat provided to a system from surrounding then it changes the internal energy ‘ΔE’ of the system and the system does work ‘W’ by lifting the piston up. q= ΔE+W q is positive if heat is absorbed, negative if heat is released W is positive if work is done by the system, negative if work is done on the system Q#6 (b) Page#163 In a certain process 848 J of heat is absorbed by a system, while 394 J of work is done on the system. What is the change in the internal energy for the process? Q#7 (a) Page#163 If 1800 cals, pf heat is added to a system while system does work equivalent to 2800 cals by expanding against the surrounding. What is the value of ΔE for the system? Q#7 (b) Page#163 In a certain process, 500 J of work is done on a system which gives off 200 J of heat. What is the value of ΔE for the process? Derivation Pressure – Volume Work Equation Consideration: Consider a cylinder of a gas having an area of cross section ‘A’ fitted with a frictionless and weightless piston. Case (a) Process at constant volume Case (b) Process at constant pressure Enthalpy: The total heat content of a system is called enthalpy. It is denoted by H. H=E+PV Change in Enthalpy (ΔH): The amount of energy absorbed or released at constant pressure is called change in enthalpy (Δ H) Numerical When 4000 J heat is added to a gaseous system at a constant pressure of 101300 N/m2, its internal energy increases by 500 J. Calculate the change in volume of the system. (2015) Thermochemistry The branch of chemistry which deals with thermochemical reactions. 1 Cal=4.184 J Hess’ Law of Constant Heat of Summation Statement: “The total enthalpy change remains constant either in direct method or indirect method.” Explanation: Consider a chemical reaction in which reactant ‘A’ changes to the product ‘D’ in a single step with ΔH as the enthalpy change. It may proceed through different intermediate stages i.e, ‘A’ first changes to ‘B’ with enthalpy change ΔH1, ‘B’ then change to ‘C’ with enthalpy change ΔH2 and finally ‘C’ changes to ‘D’ with heat change as ΔH3. According to Hess’ law: ΔH= ΔH1 + ΔH2 + ΔH3 Application of Hess’ law CO2 gas reacts with excess of NaOH to give Na2CO3 with enthalpy change -90 KJ/mole. This reaction may be carried out in two steps. I the first step the enthalpy change is -49 KJ/mol and in the secon step the enthalpy change is -41 KJ/mol. Hence according to Hess’s law: ΔH= ΔH1+ ΔH2 ΔH=-49-41=-90 KJ/mol Heat of Formation The change in enthalpy when 1 gram mole of a substance is formed from its elements. It is denoted by ΔHf
Since graphite is the most stable allotrope of carbon so it has been
assigned a heat formation value that is nearly equal to 0. The heat of formation of elements is equal to 0.
Standard Heat of formation (ΔH°f) at 25 °C and 1 atm.
The Born-Haber Cycle • It is the best application of Hess’s law • It states that energy change in a cyclic process is always zero. ΣΔH(cycle)=0 • It enables us to calculate the lattice energy of ionic compounds. Enthalpy of Neutralization (ΔH°n) The amount of heat evolved when 1 mole of water is formed I neutralization reaction is called enthalpy of neutralization.
Enthalpy of neutralization of strong acid with a strong base always
remain same i.e -57.4 KJ/mol. Enthalpy of Combustion It is always negative.
It is calculated by a BOMB CALORIMETER in which volume remains
constant. Spontaneous Reaction • Does not require any external aid for completion. For the start they may need energy. • The reactant releases energy in these reactions • They occur in nature. • They cannot be reversed. Example: Evaporation. Example: water flowing down the hill. Example: Neutralization Example: CuSO4 + Zn ZnSO4 + Cu Example: burning of coal Non Spontaneous Reaction • Water pumping up the hill. • Refrigeration • Haber-Bosch Process
“Foundations to Flight: Mastering Physics from Curiosity to Confidence: Cipher 4”: “Foundations to Flight: Mastering Physics from Curiosity to Confidence, #4