Chemical Energetics: The branch of science which deal with energy change in physical and chemical reactions.

System: A specified portion of universe which is under observation is called system. It is of two types: (i) Heterogeneous system: If all the parts of the system have different physical and chemical properties. (ii) Homogenous system: If all the parts of the system have same physical and chemical properties. Surrounding: The rest part of the universe which is not under investigation. Type of system: 1.Isolated: A system that can not exchange energy or matter from surrounding. 2. Close system: It can exchange energy only with surroundings. 3. Open system: It can exchange both energy as well as matter with surroundings. State variables: The measurable properties required to describe the state of the system example; temperature, pressure, volume. State function: A state function is a property of the system whose value depends only upon the state of the system and is independent of the path by which the path is reached. Mode of transference of energy: In energetic two main mode of transference of energy are: (i) Heat change: Energy is always exchanged with surrounding except in case of isolated system when there is change in temperature between system and surroundings. (ii) Work done: It is exchange of energy of system with surrounding when there is change in pressure. Internal energy of system; it is the sum of all different kind of energy associated with molecule such as energy of translation ,rotation ,and vibration, electric energy ,energy due to molecular interaction. Internal energy change: it is difference between energy of reactant and product. It may also be defined as amount of heat evolved or absorbed in chemical reaction at constant temperature and at constant volume. It is denoted by E. E=Eproduct-Ereactants Enthalpy (H): it may be defined as amount of heat evolved or absorbed in chemical reaction at constant temperature and pressure. Or, the sum of the internal energy and the product of its pressure and volume. Enthalpy change: It is measure of heat change taking place during a process at constant pressure. H=E+PV and H= E+P V Enthalpy of reaction: The change during a chemical reaction when number of moles of reactants and product being same as indicated by the balanced chemical equation. Enthalpy of formation: Enthalpy change when one mole of a compound is formed from its elements. Standard Enthalpy of formation: Enthalpy change when one mole of a compound is formed from its elements, all the substance being in their standard state (1 atm. and 298K) Note: By convention the heat of formation of every element in its standard state is arbitrary assumed to be zero. H0 (for the reaction) = H0 (products)-H0 (reactants) Enthalpy of combustion: The amount of heat change when one mole of a substance is completely burnt on excess of oxygen or air is called heat of combustion. Calorific value: The amount of heat produced when one gram of a substance is completely burnt. The amount of heat is taken in calories or joules. Enthalpy of solution: The heat change when one mole of substance is dissolved in a specified quality of solvent at a given temperature is called heat of solution. Enthalpy of neutralization: The heat change when one gram equivalent of acid is completely neutralized by a base or vice-versa in dilute is called heat of neutralization. Note: Heat of neutralization of all strong acids by strong bases is always -57.1KJ irrespective of the nature of acids or the base. Enthalpy of fusion: The amount of heat change when one mole of a solid substance is converted into its liquid state at its melting point. Enthalpy of vapourisation: The amount of heat change when one mole of a liquid substance is converted into its gaseous state at its boiling point. Sir. AJAY YASHPAL(98187 02707) Education Point Sir. Anoop Behl

Enthalpy of sublimation: The amount of heat change when one mole of a solid substance is directly converted into its gaseous. First law of Thermodynamics: It states that energy can neither be created nor destroyed, although, it can be exchanged from one state to another or total energy of universe is constant. Hesss law: It states that the enthalpy change in a particular reaction is always constant and is independent of the path in which the reaction takes place. This Law means that amount of heat evolved or absorbed in a chemical reaction is always constant whether the reaction is taking place in one step or in number of steps. This also means that a chemical reaction can be summed, subtracted, multiplied or divided by any constant like algebraic equations. One more conclusion can be drawn from the Hesss law that the same amount of energy is required to build a molecule from its constituents that was released or absorbed during breaking of molecules into its constituents or vice versa. Some main uses of Hesss law: 1. Determination of enthalpy of formation: It is a very useful property or use of Hesss law because there are so many compounds which can not be made from their constituent elements. For example; Benzene, polyethylene, sugar, etc. 2. Determination of enthalpy of transition: It means energy evolved or absorbed during change in physical state of any substance. For example: conversion of liquid to gas or vapours, changing crystal structure. Predicting enthalpies of various reactions: As stated earlier, chemical equations can be summed, subtracted, multiplied or divided by any numerical factor.

3.

Determination of Bond energy: Bond energy is the energy required to break the bonds below the atoms in a molecule in gaseous state. It is also called bond dissociation energy. Or the average energy required breaking the bonds of a given type in one mole of the gaseous molecule. Spontaneous process: The process which can take place by it self under the given set of conditions once it has been initiated if necessary for example, fall of water from higher to lower level, when a candle is lighted it remains on burning till the whole wax is not burnt, a hot body cools up to its surroundings automatically, when exposed to surroundings, etc. Note: - Spontaneous processes do not mean that the process is instantaneous or very fast, it may take a very long time for example, conversion of a dead body to fossil fuel. Non-Spontaneous process: The process, which is not spontaneous, that is which require initiation in each and after every step. For example, water gong up from lower to higher level with continuous helps of a motor, a car runs on roads if fuel is burning in its engine continuously. Driving force: The force or energy required initiating the process. Why some processes are Spontaneous and some Non-Spontaneous: Every thing in this universe tries to gain minimum energy and maximum stability are spontaneous while those going towards higher energy content or towards lesser stability are Non-Spontaneous. Why some chemical reactions are reversible in nature: There are so many reactions in nature which are reversible in nature, the reason behind that many spontaneous reactions are exothermic and if products formed are not in their maximum stable state than the heat produced will be enough for them to convert back to the reactants but all the heat can not be utilized because of heat lost so, some products always remain in the reaction mixture along with reactants this makes a reaction reversible. Do all the Exothermic reactions are spontaneous: Sir. AJAY YASHPAL(98187 02707) Education Point Sir. Anoop Behl

4.

Maximum numbers of spontaneous processes are exothermic or vice-versa, because reaction moves toward lower energy content but H is not only the criterion of spontaneity, reactions also move towards maximum randomness or disorder. So, reactions move towards: 1). Minimum energy, 2). Maximum Stability; 3). Maximum randomness or disorder. Entropy (s): The property of a system used to measure the degree of disorder or randomness of system. S = S (products) - S (reactants). Reactions move towards +ve sign. Also, S = Q / T or H / T. Q heat supplied. Its unit is jK-1. Physical meaning of entropy Entropy is a measure of randomness of system, i.e., where the randomness is higher reactions move there. As solids have ordered arrangement of particles, liquid and gaseous particles are unordered but disorder in liquid is limited but in gases it has no limit. A particle of gas can have any velocity and may be any where in the container. So, gases have maximum randomness than liquid and liquids have higher than solids. So, reactions try to move towards where gaseous or liquid products are more. Second law of Thermodynamics: It states that entropy of universe increases after every spontaneous process or natural process. Free energy: It is defined as the maximum amount of energy available to a process during a process that can be converted to useful work. OR The amount of energy that remained unused by the system after getting minimum energy, maximum stability, and maximum randomness. OR Simply, It is a measure of capacity of a system to do work. It is denoted by G. Thus, H Enthalpy change. T Temperature in Kelvin G = H -T S Entropy change. S Effect of temperature and tendency of reaction to occur in forward direction Type of reaction Exothermic Sign of H + + Sign of T S + +

Endothermic

G - (at low temp.) + (at high temp.) + + (at low temp.) - (at high temp.)

Behavior Spontaneous Spontaneous Non- Spontaneous Non- Spontaneous Non- Spontaneous Spontaneous

Standard free energy: The free energy change when the reactants are in their Standard states (i.e., at 298K and 1atm) and are converted to the products in their Std. States. Standard free energy of formation: Change in free energy when 1 mole of a substance is formed from its constituent elements in their Std. States. o o G o f G f ( products) G f ( reac tan ts ) Actually, free energy or Gibbs free energy is the amount of energy that can be used to do useful work but work may be of two types: Expansion work (Pressure-Volume work) Non-Expansion work. So, G = H - T S G = - n f Eocell {Electric work}. Sir. AJAY YASHPAL(98187 02707) Education Point Sir. Anoop Behl

Third law of thermodynamics: It states that at absolute zero temperature, entropy of a perfectly crystalline substance is zero. OR At absolute zero randomness of a perfect particle is zero

Assignment
1. Is it possible for any process to have H = E? If yes, under what conditions? If no, state why not? 2. Define the terms internal energy change and enthalpy change. How they are related. 3. Explain heat and write as the modes of transference of energy between the system and the surroundings. 4. Define the following: (a) Hesss law, (b) enthalpy of formation, (c) enthalpy of combustion. 5. Define the terms: - (a) enthalpy of fusion (b) enthalpy of sublimation, (c) enthalpy of vapourisation. How these are related to each other. 6. Define entropy and free energy of a system. Predict the feasibility of reaction when both H and S are positive. 7. Predict the sign of S (positive and negative) for the following reactions: (a) HCOOH (l) H2O (l) +CO (g) (b) NH3 (g) +HCl (g) NH3Cl (g) (c) 2O3 (g) 3O2 (g) (d) 2H2 (g) +O2 (g) 2H2O (l)

8. Criticize the statement the decrease of enthalpy is the sole criterion for the feasibility of a process. 9. What is a thermodynamical equation? Explain why it is essential the physical state of reactants and products in thermodynamical equations. 10. Can the entropy change or the randomness change alone be the sole criterion for predicting the spontaneity of a reaction? 11. What are spontaneous reactions? Give one suitable example. 12. Explain the term entropy of system. Account for the fact that entropy of ice is less than that of water. 13. What is bond energy? How is the bond energies related to change in enthalpy of a reaction? 14. Define and explain the term free energy. 15. In the following changes state whether order has increased or decrease and consequently the direction of change of entropy of the system: (1) Steam water (2) Cr3+ + 6H2O (aq) [Cr (H2O)6]3+ (aq) photosynthsesis carbohydrates + O2 (3) CO2 +H2O (4) Normal egg Boiling egg 16. What do you understand by free energy change? How is it related to enthalpy and change? How does it help in predicting the spontaneity of a reaction? 17. What are the two main tendencies which act as driving force for a reaction? Discuss the influence of temperature on spontaneous processes.

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Sir. Anoop Behl

Numericals 1. As system gives out 30j of heat and does 75j of work. What is the internal energy change? 2. A system absorbs 470j of heat and does work equivalent to 200j on its surroundings. Calculate the change in internal energy. 3. During the process, a system absorbs 710j of heat and does work. The change in internal energy for the process is 460j. What is the work done by the system? 4. The reaction between gaseous hydrogen and chlorine is H2 (g) +Cl (g) 2HCl (g), H = -184.0 Kj (a) what is enthalpy of formation of HCl (b) How much heat will be liberating at 298K and 1atm for the formation of 365gm of HCl? 5. The enthalpies of combustion of C2H2 (g) and C2H6 (g) are -130KJ and -1561.5KJ respectively. The enthalpy of formation of liquid water is -286KJ.Calculte the enthalpy change for C2H2 (g) +2H2 (g) C2H6 (g). 6. Calculate the heat of combustion of glucose from the following data: C (graphite) +O2 CO2 (g); H= -395.0KJ H2 (g) + 1 2 O2 (g) H2O (l); H=-269.4KJ 6C (graphite) +6H2 (g) +3O2 C6H12O6 (g); -1169.9KJ 7. The heat change for the reaction N2 (g) +3H2 (g) 2NH3 (g) is -92.2KJ. Calculate the heat of formation of ammonia. 8. Calculate the heat change for the reaction CH4(g)+2O2(g) CO2(g)+2H2O(g).If heat of formation CH4(g),CO2(g),and H2O(l) are -74.8,-393.5 and -285.8 KJmole-1 respectively. 9. The H0 for the reaction, 4S(s) +6O2 (g) 4SO3 (g) is -1583.2 KJ. Calculate Hi of the sulphur trioxide. 10. The heat formation of Fe2O3(s) is -824.2KJmole-1. Calculate the heat change for the reaction: 4Fe(s) +3O2(g) 2Fe2O3(s) 11. The standard molar heat of formation of ethane, carbon dioxide and liquid water are -21.1, 94.1, and -68.3 Kcal respectively. Calculate the standard heat of the following: 2C2H6(s) +7O2 (g) 4CO2 (g) +6H2O (l). 12. Calculate the heat of formation of ethane from the following data: C (graphite) +O2 CO2 (g); H= -395.0KJ H2 (g) + 1 2 O2 (g) H2O (l); H=-285.8KJ C2H6 (g) + 7 2 O2 (g) 2CO2 (g) + 3H2O (l); H=1560.0KJ 13.Calculate the heat of formation of acetic acid (CH3COOH) if its heat of combustion is -867 KJmole-1 .The heat of formation of CO2(g) and H2O(l) are -393.5 and -285.9 KJmole-1 respectively. 14. Calculate H0 for the reaction CO2 (g) +H2 (g) CO (g) +H2O (g). Given that, H0 for CO2 (g), CO (g) and H2O (g) are -393.5, -111.3, and -241.8 KJmole-1 respectively. 15. The heat formation of C2H2OH (l), CO2 (g) and H2O (l) are -277.0,-393.5, and -285.8 KJmole-1 respectevely.Calculate the heat change for the reaction: C2H5OH (l) + 3O2 (g) 2CO2 (g) +3H2O (l). 16. The heats of combustion of CH4 and C2H6 are -890.3 and -1559.7 KJmole-1respectevely.Which of the two has greater efficiency of fuel per gram? 17. Sucrose undergoes combustion as: C12H22O11 (s) + 12O2 (g) 12CO2 (g) + 11H2O (l) +5645 KJmole-1 (i) How much energy will be liberated when 51.3gm of sucrose is burnt? (ii) What is the energy required for the production of 5.472gm of sucrose? 18. The heat of formation of CH4, C2H6and C4H10 -74.8,-84.7 and -126 KJmole-1 respectively .Arrange them in the order of their efficiency as fuel per gram of heat of formation of CO2 (g), 7H2O (l) are -393.5 and -285.8 KJmole-1 respectively. 19. Which of Aluminium and hydrogen has greater efficiency per gram if 2Al(s) + 3 2 O2 (g) Al2O3(s); H=-1667.8KJ 1 H2 (g) + 2 O2 (g) H2O (l) H =-286.9KJ Sir. AJAY YASHPAL(98187 02707) Education Point Sir. Anoop Behl

20.The standard heat of formation of CH4(g),CO2(g) and H2O(g) are -76.2,-394.8 and -241.6 KJmole-1 respectevely.Calculate the amount of heat evolved by the burning 1m3 of methane measured at N.T.P. 21. Estimate the average S-F bond energy in SF6. The value of standard enthalpy of formation of SF6 (g), S (g) and F (g) are -100, 275, and 80 KJmole-1 respectively. Answers: -105J 270j -250j -92.0Kj, -920Kj -312Kj -2816.6Kj 46Kj -1 -1 -890.3Kjmol -395.8Kj -1648.4Kj -744Kcal -84.4Kj -481.8Kjmol 40.4Kj mol-1 -1367.4Kj CH4 846.75Kj 90.32Kj CH4>C2H4>C4H10 Hydrogen 35974.6Kj 309.16Kjmol-1

Sir. AJAY YASHPAL(98187 02707) Education Point

Sir. Anoop Behl