Soe, eo wk GILBERT W. CASTELLAN PHYSICAL JH EMIS PRY THIRD EDITIONTo Joan and our family Sponsoring Editor: Robert L. Rogers Production Editor: Margaret Pinette Copy Editor: Jerrold A. Moore Text Designer: Debbie Syrotchen Design Coordinator: Herb Caswell Mlustrators: VAP International Communications, Ltd. Cover Designer: Richard Hannus, Hannus Design Associates Cover Photograph: The Image Bank, U. Schiller Art Coordinator: Joseph K. Vetere Production Manager: Herbert Nolan The text of this book was composed in Monophoto Times Roman by Composition House Limited. Reprinted with corrections, November 1983 Copyright © 1983, 1971, 1964 by Addison-Wesley Publishing Company, Inc. All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the prior written permission of the publisher. Printed in the United States of America. Published simultaneously in Canada. Library of Congress Catalog Card No. 82-74043. ISBN 0-201-10386.994 The Laws of Thermodynamics “Jost” by the turbine. Similarly, in the last example, the mechanical energy produced by the motor, plus the friction losses, is exactly equal to the electrical energy supplied to the motor from the power lines. The validity of this conservation law has been established by many most careful and painstaking direct experimental tests and by hundreds of thousands of experiments that confirm it indirectly. The first law of thermodynamics is the most general statement of this law of conserva- tion of energy; no exception to this law is known. The law of conservation of energy is a generalization from experience and is not derivable from any other principle. 6.2 RESTRICTIONS ON THE CONVERSION OF ENERGY FROM ONE FORM TO ANOTHER The first law of thermodynamics does not place any restriction on the conversion of energy from one form to another; it simply requires that the total quantity of energy be the same before and after the conversion. It is always possible to convert any kind of energy into an equal quantity of thermal energy. For example, the output of the generator can be used to operate a toaster im- mersed in a tub of water. The thermal energy of the water and the toaster is increased by just the amount of electrical energy expended. The electric motor can turn a paddle wheel in the tub of water (as in Joule’s experiments), the mechanical energy being converted to an increase in the thermal energy of the water, which is manifested by an increase in the temperature of the water, All kinds of energy can be completely transformed into thermal energy manifested by an increase in temperature of some sample of matter, usually water. ‘The quantity of energy involved can be measured by measuring the temperature rise of a specified mass of water. Energy may also be classified according to its ability to increase the potential energy of a mass by lifting it against the force of gravity. Only a limited number of the kinds of energy can be completely converted into the lifting of a mass against gravity (for example, the mechanical energy produced by the electric motor). The thermal energy of a steam boiler or the chemical energy of a compound can be only partly converted into the lifting, ofa mass. The limitations on the conversion of energy from one form to another lead us to the second law of thermodynamics. 6.3 THE SECOND LAW OF THERMODYNAMICS Imagine the following situation. A hard steel ball is suspended at a height h above a hard steel plate. Upon release the ball travels downward losing its potential energy and simultaneously increasing its velocity and hence its kinetic energy. The ball hits the plate and rebounds. We assume that the collision with the plate is elastic; no energy is lost to the plate in the collision. On the rebound the ball travels upward, gaining in potential energy and losing kinetic energy until it returns to the original height h. At this point the ball has its original energy, mgh, and its original kinetic energy, zero. We can either stop the motion at this point or let the ball repeat the motion as often‘as we please. The first law of thermo- dynamics in this case is simply the law of conservation of mechanical energy. The sum of the potential energy and the kinetic energy must be a constant throughout the course of the motion. The-first law is not in the least concerned with how much of the energy is potential or how much is kinetic, but requires only that the sum remain constant.PHYSICAL CHEMISTRY THIRD EDITIONCover Desig: Bie DeCiceo Cover image: © iStockphoto Eaevier Academic Press 30 Corporate Dive, Suite 400, Burlington, MA 01803, USA. 5258 Street, Suite 1900, San Diego, CA92I01-4495, USA. ‘84 Theobuls Road, London WCIX SRR, UK “Tis book sprinted on ai-e paper. ©) CCopyrighe © 2008, ever Inc. Al rights reserved, [No partof this publication maybe produced or tansminad in any feemor by any means, ‘ecttonic or mechanical, inclaling photocopy, recording, or any information storage Snd retrieval system, without permieson in siting from the pubisher Perrcsion maybe sought recy tom Exes Sonos & Techrsogy Fights Deparment in (Odor, UK: pane (nd) 186564380, ta (+4) 1885 853039, € ret peminsens@ lander cae ‘You may asa complete your equet amine va he Elsevier homepage (hp ese comy by setecing Customer Suppo” anathen“Oataning Peemesens” Library of Congress Catalogin-Publising Data ‘Morimer. Robert Physical chemistry / Robert G. Mortimer. Sede Pen. Includes bibliographical references sn index. ISBN 970-12-370617-1 (handover: alk. popes) 1. Chemistry, Physical and theoretical. Tie ‘QDs53.2 M6? 2008 Sti-de22 2008007675 ‘tsh Library Cataloguing in Publication Data [catalogue record for this book available from the British Library ISBN13:978-0-12-370617-1 For information onal Bnevier Academic Press pobicatons ist our Web teat we hooksleeviercom Printed in Cada of 0910987654321 Working together to grow libraries in developing countries sewelievercom | wowehookaidorg | worwstbeeorg22 Heat 51 ‘Obvain a formula forthe work done in reversibly and isothermally compressing 1.000 mol of a gas froma volume V; wa volume Vs ithe gas obeys the Redlich-Kwong equation of state ‘Using the formala from para ind the work done in ‘everibly compressing 1.000 mol of carbon dioxide foe 10.00 to 5.0001 at 298.15 K. Compare with the result obtained by assuming thatthe gas is ideal €. Using the formala from para, calculate the work done ‘on the surroundings if 1.000 mol of carbon dioxide ‘expands isothermally but iereversibly from 5.000 Lo 10.01. atan extemal pressure of 1,000 atm. Compare with the result obtained by assuming that the gas is ieal ‘Obvain a formula forthe work done in reversibly nd ‘sothermally compressing 1.000 mol of a van der Waals ‘2 froma volume V toa volume V3 Using the formal from par a find the work done in reversibly compressing 000ml of carbon dioxide Heat ‘from 10.00 to 5.000 Lat 298.15 K. Compare withthe ‘result obtained by assuming thatthe gasis ideal ‘Using the formala from part, calculate the work done ‘on the surroundings if 1.000 mo of carbon dixie ‘expands isothermally but irreversibly from 5.000 L to 1000 atan extemal pressure of 1,000atm, Compare with the result obtained by assuming thatthe gasses 2.8 Test the following differential for exactness a Par + vv Be setrde + ye%dy e ndrt bedy 2.9 Cay out he line integral: [(ar-5e#) ‘on the path fom (300.0K, 10.01) 10 (300.0, 20010 (400.0K, 20.01). Take m = 1.000 mol Joseph Black was the first to distinguish between the quantity of eat and the Joseph Black, 1728-1798, was a ‘Scotish chomst who ciscovered ‘carbon dioxide (xed air) by heating ‘alctim caronate death. “intensity” of heat (lemperature) and wo recognize latent heat absorbed or given off in phase tramitions. However, Black believed in the caloric theory of heat, Which incorrectly asserted that heat was an “imponderable” uid called “calor ‘This incorrect theory was not fully discredited until several decades after Black's Heat Transferred during Temperature Changes A small amount of heat adie to system is proportional to its change in temperature ‘of the system if there is no phase change or chemical reaction: dg =Car 2 where dg isan infinitesimal amount of heat transferred othe object and.d7 isa sulting infinitesimal change in temperature. The proportionality constant Cis called the heat ‘capacity of the system, Equation (22-1) does not indicate that Cis a derivative of g with respect to T. We will see that cy ian inexact differential so thatthe heat capacity C depends onthe way in which the temperature of the system is changed. Ifthe temperature is changed at ‘constant pressure, the heat capacity is denoted by Cp and is called the heat capacity at ‘constant pressure. I the temperature is changed at constant volume, the heat capacity is denoted by Cy and is called the heat capacity at constant volume. These two heat ‘capacities are not generally equal to each other.2 Work, Heat, and Energy: The First Law of Thermodynamics ‘The specific heat (better called the specific heat capacity) is denoted by ¢ and is a a cecal (9) a2 ‘where mm is the mass of the object. For a pure substance the molar heat capacity is denoted by Cy and is defined as the beat capacity divided by the amount of the substance measured in moles. We will use both the molar heat capacity at constant = 7 @) oa as one(®) ame ‘where 1 isthe amount of the substance in moles. Both of these molar heat capacities are intensive variables, Its an experimental fact thatthe heat capacity of any object is ‘always postive. There is no such thing as a system that lowers its temperature when thea is added wit ‘fan object is heated from temperature T to temperature T> without any chemical reaction or phase change occurring, the quantity of heat transferred to the object is given by n o= [ae fro eas) te a pct nnn tempt n acl dT =C(Ty-)) =CAT (ifC is independent of T) (22-6) A positive value of qinliates heat transerrel wo the system and a negative value Indicates heat transfered from he system ots surroundings ‘The calorie was the fst metric unit of beat and was originally defined asthe amount of heat required to raise the temperature of 1 gram af liquid water by 1°C 31 15°C. The specific heat capacity of liquid water equals .00cal K!~! at 15°C. “The heat capacity of liquid water is nearly temperatur-independent and we can vse tis value for any temperature wih good accuracy. The calorie is now defined 10 equal 4.1841 (exacly) so that heat capacities can be expessd in joules as well asin calories4 2 Work, Heat, and Energy: The First Law of Thermodynamics Heat Transferred during Phase Changes ‘When a phase change occurs, heat can be transfered to or from the system without changing its emperature or its pressure. This heat is sometimes called laret heat. The amount of latent heat per unit mas is characteristic ofthe substance ad the phase teansition The latent heat of fusion nching) is denoted by Auf For water at O°C and a constant pressure of 1,000atm Aga! equals 79.72calg~'. The latent heat of ‘vaporization (oiling) is denote by Ag For water a 100°C and 1.000 at AH ‘equals $39°8Seal g-. PROBLEMS ‘Section 2.2: Heat 2:10 Calculate the amount of heat required 1 bring 1.00001 ‘of water from solid at 00°C to gas at 100.0°C ata ‘constant presse of 1000 atm, Calculate w forthe process. 2:11. Compute the rise in temperature of water fit is brought 10 restate falling overa waterfall $0.0m high. Assume that ‘no heats transferred to the surroundings 2.12 The normal boiling temperature of ethanol is 78.5°C, and ity molar enthalpy change of vaporization at this temperature is 40.313 mol™!, Find g and w if 3.000mol of ‘ethanol are vaporized at 785°C anda constant pressure of, 1.00030. 2.19 a, Ifa sample of 2.000 mol of heliam gas isothermally and reversibly expanded at 298.15K froma pressure . Ifthe sample of helium from pat a imeversibly expanded from the same initial state to the same final state with Pas = 1.000atm, ind wand 4. 2.14 Calculate q and w if2.000 mol of beim is heated reversibly froma volume of 20.0 and a temperature of 300.0K to. volume of 40.01. anda temperature of (600.0K. The heating is done in such a way that the temperature remains proportional to the volume, 2.15 The norma boiling emperatur of ethanol is 78.5°C, and {ts molar enthalpy change of vaponzation a his tempentur is 403k) mel! Find g and w if 3.000 m0 of ‘thaol ae eves vaporiad at 75°C anda constant23 Internal Energy: The First Law of Thermodynamics 55 Pressure of 1,000 atm. Neglect the volume ofthe Liquid 'b Assume that Cp is piven by the formula in Table A.6 compared with that ofthe vapor. A sample of 2.000 mol of CO> gas is heated fom 0.00°C wo with the parameters given there and thatthe sis “described by the truncated pressure vieial equation of 100.0°C ata constant pressure of 1.000 tm. Find g and w - for this process. State any assumptions or approximations. ae ae ‘4, Assume that Cpa is constant and equal its value in ‘Table AS a 298 15 K. Assume thatthe gas is ideal, and use the fat that A = Ba. ‘Benjamin Thompson. Count Rumford, 1753-1814, was an American _Britsh phystist who abandoned his family and let America aferthe “American evotuion because of his royals sympathies. Ho pursued a ‘checkered careerinvarcus countries, ‘including Bavaria (where he ingtioted ‘inset withthe Elector of Bavaria), France (where he marred Lavoisier widow), and England (where he founded the Royal insttuson and hired ‘Humphrey Davy asa lecture). Juus Robert Mayer, 1814-1878, was a German physicist originaly vained as a ‘hysician. He was apparently the fst to ‘25307 that heal and work are vO diferent means ty which energys transtered. and tat energy can neither ‘be created no destroyed Internal Energy: The First Law of Thermodynamics Although Lavoisier discredited the phlogiston theory of combustion, which held that ‘combustion was the loss of an “imponderable” Auid called phlogistn, he was one of the principal promoters of the equally incorrect caloric theory of heat espoused by Black, which asseted that heat was an imponderable fluid called “caloric.” The first ‘experimental studies tat discredited the caloric theory were done by Count Rumford. Rumford wast onetime in charge of manufacturing cannons forthe Elector of Bavaria, theruler who made him a count, Rumford noticed that when a canon was bored with dull boring too], more heat was produced than when a sharp tool was used. He caried ‘out a systematic set of experiments and was able wo show by using avery dal ool that there was noapparent limit tothe amount of heat that couldbe generated by friction. He immersed the cannon in water to transfer the heat from the cannon and even generated ‘enough heat to have melted the cannon. Rumford’ results showed that “cleric” was ‘ot simply being extracted from the cannon, because if caloric existed only a definite amount could be storedin acannon without meting it. Work must have been converted tobeat, Rumford calculated an approximate value for the “mechanical equivalent of heat.” ‘or the amount of heat to which a joule of work could he converted. Better values were obtained by Mayer in 1842 and Joule in 1847. Joule carried out experiments in Which changes of temperature were produced either by doing work on a system or by heating it. His apparatus is schematically depicted in Figure 24. A falling mass tumed a stirring paddle in a sample of water, doing work on the quid. The rise in temperature of the water was measured and the amount of work done by th falling ‘mass was compared with the amount of heat required to produce the same change in temperature, Joule found that the ratio of the work to the amount of heat was aways the same, approximately 4.18 J of work for 1 00 cal of heat. The calorie is now defined tobe exactly 4.184).A Textbook of Physical Chemistry K K Sharma © L K SharmaVIKAS® PUBLISHING HOUSE PVT LTD E28, Sector-8, Noida-201301 (UP) India Phone: +91-120-4078900 « Fax: +91-120-4078999 TRAS' Registered Office: Vikas Publishing House Pvt. Ltd, 7361, Ravindra Mansion, Ram Nagar, New Delhi E-mail: helpline@vikaspublishiing.com + Website: wiww.vikaspublishing.com ‘SALES AND BRANCH OFFICES OF VIKAS* AND S. CHAND & COMPANY PVT. 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No part of tis publcaion which is material protected by Wa copyright notice may Be reproduced or Wansmnlied or vlized ‘or stored in ay form of by any means now known of hereinafter Invented, electronic. cigtal of mecraniea, ineuding photocopying, scanning, recoraing oF by any information storage or etneva system, sthout por wren permission Kom the publisher Information contained in this book has been publahed by VIKAS® Publishing House Pvt Lid and has been obtained by its Autos fom sources believed o be reliable and are corect othe best of their knowiedge. However, the Publisher and ts Authors shal in no event be liable for any ‘errors omissions or damages arising out of use of his information and specticaly disci any impled warranties or merchantablty o fies for ‘any particular use. Disputes if any are subject o Delhi Junsdicton ony. Printed in india.A Textbook of PHYSICAL CHEMISTRY For BSc Students of all Indian Universities Under CBCS. Sixth Edition Late K K Sharma Department of Chemistry Zakir Husain College University of Delhi LK Sharma Former Associate Professor Departmenat of Chemistry ARSD College University of Delhi 5 VIKAS VIKAS® PUBLISHING HOUSE PVT LTDThermochemistry 173 7.5 HEAT OF FORMATION The thermal change involved in the formation of 1 mole of a substance from its elements is known as the heat of formation of the substance. If the reactants and products involved in the reaction are in the standard state (281 K and 1 atm), the heat change is referred to as the standard heat of formation. In measuring heat of formation, a number of difficulties arise. To get around some of the difficulties, an assumption is made that the enthalpies of all elements in their standard state at 25°C are arbitrarily taken to be zero. If an element exists in more than one allotropic form under these conditions, the form most stable at 1 atm and 25°C is taken to have zero value. Suppose you were to design an experiment to determine the heat of formation of carbon dioxide (q°) which is defined by the equation Co + Og) > COng Paxkd In principle the method looks quite simple. You might decide to take a known weight of carbon and burn it in a steam of oxygen, transferring the heat to a calorimeter so that it can be measured. Now an important question arises— which allotrope of carbon will you choose and will the heat depend on the allotrope. Experiment shows that it does matter and in the case of carbon, graphite C,,, and diamond C,, to give different results, ie., 393.51 kJ mole 395.41 kJ mole Cyt Oy) 2 C0, Cea * Ong > COny ts From the equation 2Mg,,+0,,, > 2MgO,, gq? =x kd Calculate the standard heat of formation of magnesium oxide. ‘The equation shows that x kJ accompany the formation of two moles. Therefore the standard heat of formation will be x/2 kJ. It is often possible to measure a heat of formation directly because the reaction will not work. If we want of find the heat of formation of potassium sulphate, we cannot put the elements together and measure the heat produced. The reaction, will not work. It is because of this reason many heats of formation must be calculated using Hess’s law. 2K, +S, + 20,4, > KS0y, P= y kd Generally speaking a compound that has a large heat of formation is unstable and one with a negative heat is stable. Consider the thermal stability of the hydrides of the halogens. When hydroiodic acid is warmed it breaks down quite readily forming appreciable quantities of hydrogen and iodine. 2HI > H, + 28) Hydrogen bromide is more stable and hydrogen chloride is most stable. It is most important to distinguish between chemical reactivity and thermal stability. You will see that while calcium carbonate has a very low heat of formation, so that we would predict a high stability for it, ie., the reaction, 2CaCO,,, > 2Ca,, + 2C,, + 30,,,Thermochemistry 177 7.7 HEAT OF NEUTRALIZATION When aqueous solution of acids and bases react, heat is evolved. The change in enthalpy when one gram equivalent of an acid is neutralized by one gram equivalent of a base in dilute solution is known as the heat of neutralization of the acid. It has been shown that the heat of neutralization of any strong acid by a strong base is practically the same as shown in the following reactions. HCl,,, + NaOH, > NaCl,,,, + H,O AH =~ 13.7 kcal HNO,,,,. + NaOH,,, > NaNO,,,,, + H,O AH =~ 13.7 kal ‘The constant value of —13.7 kcal for the heat of neutralization of a strong acid with a strong base indicates that the same chemical change is taking place in all these reactions. The neutralisation of hydrochloric acid by sodium hydroxide can be symbolized as: H’ + Cl + Nat + OH: > Na* + Cl +H,0 or H*+OH > H,0 AH = -13.7 keal Hence, every neutralization reaction involves the combination of H* and OH- ions to form unionized water. However, the heat of neutralization of a weak acid or a weak base is not constant. This can be explained on the ground that in such cases, in addition to neutralization, the ionization or dissociation of the weak acid or the weak base also takes place. For example, the neutralization of acetic acid by sodium hydroxide solution CH,COOH + NaOH > CH,COONa + H,O AH =~13.25 keal eT) is in reality a two-stage process: CH,COOH == CH,COO-+H' AH, =D (7.2) where D is the heat of dissociation and H'+OH 3H,O — AH=~13.7 kcal (7.3) ‘The sum of equations (7.2) and (7.3) gives equation (7.1). Consequently, -13.25 =D +(-13.7) or D=+0.45 keal Hence, the heat of ionisation or heat of dissociation of a weak acid or a weak base can be determined from the heat of neutralization data. Problem 7.5. ‘The heat of neutralisation of hydrocyanic acid by sodium hydroxide is —2.90 keal/gm-equivalent at 25°C. Calculate its heat of ionization. Solution. ‘The given reaction is HCN + OH" > CN’ +H,0. Let AH, be the heat of ionization of hydrocyanie acid, HON == H+ CN H+ OH > H,0180 A Textbook of Physical Chemistry 7.9 HEAT OF COMBUSTION The heat of combustion of a compound or element is the change of heat content when one mole of it is burnt in oxygen at constant pressure. ‘The heats of combustion depend on the conditions of burning. For example, if water is the product of combustion, the heat evolved will depend on whether it is in the liquid or vapour form. Thus, it is essential to state the conditions of combustion and to have a standard heat. If one mole of a substance is completely burnt into oxygen, reactants and products being at 298K and 1 atm, the heat evolved is referred to as the standard heat of combustion. Standard heat of combustion are usually stated by means of an equation, for example. =6CO,,, + 3H,O,, AH? = LOg 781.0 keal CHan + 73 On This means that when one gram molecule of benzene is burnt in excess of oxygen, 781 kcal of heat is given out. The heat of combustion can be determined experimentally in a Bomb calorimeter. The general form of this apparatus is shown in Fig. 7.1. ‘The substance whose heat of combustion is to be determined is placed on the platinum support and above it the two platinum wires are joined by a thin spiral of iron wire. ‘The bomb is closed and oxygen is introduced oF till the pressure inside the bomb is about 25 Oxygen 1 atmospheres. The electric spark is then produced inlet —> by which a large amount of heat is produced. This will raise the temperature of the water around the calorimeter. To start with, the apparatus is calibrated by the measurement of temperature rise resulting from the combustion of a sample with a known heat of combustion. Generally a known weight of benzoic acid is taken, the heat of combustion of this compound being accurately known ae In organic chemistry, the combustion reactions are of outstanding suitability. The heat of combustion is also of great practical Figure 7.1: Combustion bomb significance. Fuels are bought on their calorific values. The energy providing foods are classified by the amount of heat they liberate when they are ‘burnt’ in the body. It has been observed that substances whose molecules contain the same atoms and similar linkages, have heat of combustion that are very nearly the same. This idea can be utilized for establishing the structure of organic compounds, 7.10 VARIATION OF HEAT OF REACTION WITH TEMPERATURE ‘The heat of a reaction, calculated from a table of standard heats of formation or obtained calorimetrically, corresponds to some one definite temperature. As reactions are carried out at various temperatures, it is very frequently necessary to know heats of reaction at temperatures, other than those at which they were determined. Consider a general reaction: