Principles of Physical Chemistry

1404 Pages·2013·70.474 MB·English

by  B.R. Puri, L.R. Sharma, M.S. Pathania

Comprehensively Covering the B.Sc. and M.Sc. Syllabi Prescribed by the UGC
Also catering to th~ ne11f!; .;istudents apptraring i~iarious cainpeti(i~e-~xa .
Late B.R. PURI
M.Se-, Ph.D" F.R.I.C, F.NA,
Professor of Physical Chemistry,
Panjao University, Chandigarh
1.R, SHARMA MADAN S. PATHANII\-
M.Sc., Ph.D .. fR.tC. (London). • 'M-Sc., Ph.D_ (Wllst Viiyinia University, U.SA). ·
foonerly, Professor of Physical Chemistry, Formerly, Professor of Physical Chemistry.
Department of Chemical Engineering & Technology, Panjab University, Chandigarh
Panjab University, Ch_andigarh
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46th
PREF ACE TO THE EDITION
'This is the Golden Jubilee Year of the publication of the Principles ofP hysical
Che;mistry and the occasion calls for some kind of celebration. It is a matter of
immense pleasure and satisfaction that this text has successfully retained its
prestigious position for five decades (the first edition of the book appeared in l 962}.
Thjs has been due to the fact-that we have been reyising the book almost every year to
highlight modern topics. At several places the text has been thoroughly revised.
Physical chemistry ·is traditionally divided into three parts-structure,
equilibrium, change-and usually taught in that sequence though certain topics
~annot be neatly accom_modated in this scheme. The syllabus suggested by the UGC
broadly conform"s to this pattern and we have produced a text"whicli"deals with the .
subject in a rigorous and comprehensive way to cater to the needs of the graduate and
post-graduate students of physical chemistry in the Indian universities and colleges.
The significant feature of this edition is that two new chapters have been ad_ded:
Quantum mechanics is· dealt with in three chapters, instead of the earlier two, and
statistical thermodynamics is spread over two chapter_s. Some material has been
shifted at several places within the chapters to maintain continuity and impart
lucidity and simplicity to the treatment. Structure dominates science and chemistry
is no exception. And quantum mechanics and spectroscopy are the chemist's tools to
deal adequately with structure. Complete quantum mechanical treatment of the
hydrogen ·atom, with special e.mpliasis ~n the detaikd solution of the S"chr6dinger
equation, has been given·. The radial equation and the spherical harmonics have a·t
last received the emphasis they really deserved. Also, the approximate methods. fqr
. the wave mechanical treatment of many-electron atoms have been updated. The_
perturbation theory,--both non-degenerate and degenerate-has been adequately
dealt with· and applied to the (ii-st excited state of hydrogen atom. Several other
modern topics which were earlier wr_itten as.Appendices <?r Further information
have been shifted to where they properly belong in the text The treatmento_fangular
momentum and atomic spectra is fairly comprehensive; the inessential details have
been avoided. Several solved examples have been added.
The partition function dominates statistical thermodynamics even as the
wavefunction is of paramount importance in quantiun mechanics. The chapter on
statistical thermodynamics centres around the partition function derived from
quantum mechanics. The new chapter on classical statistical mechanics builds on
the concepts of phase space and Gibbsian ensembles and rederives results already
known from conventional thermodynamics.
We have deliberately highlighted the uew material to show where physical
chemistry is going. It has benefited from developments in physics and mathematics.
Phi~Yfal chemistry has, in f~ct,
-·~-~.the,~iiJ1l~~f1r~shc~l1¥p~a~~ed
and the lifosci~j)~ett9~~1#a,C~~tiC(!.l,~ I; 1t,r!1,;'.><.~·. ~·''".;,\:l'tJ:'f+",·~.'
felt On biology;: engifl~riilg; :materials SCJ:en,ce;- u,u,.v~yt,i\1'
technology. T~ereJiM'~i~ii~g t4~ fact
edifice whose rang~ i~'tl1liyfo.terdiscipHnary,
. <<,:. '"· ·:o,. '"-,, . -· ·._ ,.,,
We make no da,im.{9r 9£igajllfjty -~ffreatment. Original books are by
ror
excellent teachers andJ~iii'e~t're'sharcher~\ we have all the regard their excellence
and eminence. (These qualities are unfortunately conspicuous in us by.their absence,
However, we are very ent1iµsia.~tic,ab~1,1tchelllistry). We have attempted to buil.d Oll.
their legacy by incorporatirig about rtirie hundred solved examples in all the chap)ers.
These examples illlli!trate andtilluin~ate t!le6ret(cal concepts and are, indeed, Jhe
an
distinguishing feature ofthis book .. ,'f,he .. r~adei: is urged to mast~r them to have
adequate understanding oft he subject._· Itg¢~!\without saying that without the available
goldmine 0f definitive infbnnation list~;_r:i;the bibliography it would not have been
possible to write this book The bibliography is fairly representative and lists some of the;
further
best and modem books for reading. Great books fascinate us for they are a
perennial source of eti.te~inment, 16.~truction and edification. The chapter-end
material is limited to review questions and simple problems.
Several teachers and students have. over the years been sending their valuable.".
suggestions for the improvement of the text.to keep it upto date. Their feedback has
, tremen~ously helped-us in iatroducing.novel innovations in the book. We take this
Qpi)Oi:tunity to thank them and hope that .they would judge our efforts indulgently and -
continue obliging us with their constructive criticism in future also. We take pleasure in
recording oi.1r sincerest thanks to l\.1/s Vishal Publishing Co., our efficient publishers, for
their courtesy, full cooperation and determiQation to go with us to any length in.
publishing the book to our entire satisfaction.
August, 2012 AUTHORS
LR. Sharma, 88/17, Panchkula (Haryana) M.S. Pa\hani~. 3621{f%~~h~~la(~1···
Ph. 0172-2560892 · Ph. 0172~2~~¥081
Quantmuemch a(nowir.ac vsme e dla(n3i7-).c s)
Chapter Pages
Postuolfqa utaenmste ucmh a(n3i9c)s
ThSec hrowdianevgqeeu ra tion (40)
0.MAlhEMACTOiNCCAEIP TS 1-20 Operaitnqo urasnm teucmh a(n4i3c)s
Cursvkee tclhiingnergaa,raph rsslo, pwie s Soluottfih Soecn h rowdaiveqneuag teirfo osnro me
Incliannsadlt oiopafole ni (n1e) .s imspylset (e4m5s)
Cursvkee t(c2h)i ng Partiianoc nlee- dimboexn( s4i5o)n al
Funcotfiar o envasal r i(a2b)le Partiiantc hlree e-dibmo(ex5n 2s)i onal
Differ:eT nhDteei raitoviafaofti nuvnec( t4)i on One-dimseinmspiloen aohlsa crimlolnaitco r (54)
Differfeonrtm(iu4al)ta iso n Rigriodt( 6o3r)
Maxiamnmadi n(i5m)a ThSec hrodeiqnugaeftrohi ryo dnr aotg(oe6mn5 )
Pardtiifafle r(e7n}t iation Angumloamre nitqnuu ma nmteucmh a(n5i9c)s
()cli(c8 )r ule Zeemealnf( e8c4t)
Integration (8) Pauelxic'ls·pu rsiino(cn8i�p).l. e
.
Methoofid nst e(g9r)a tion Physiinctaelr portfeh hteya dget;nia�otnoo mr bitals
Integfroartm(iu9ol)na s (86)
Permutaantcdio omnbsi ·n(a 1t1i)o ns Fisnter uictnth uhery ed raotgosempn e c(t8r7u)m
Fundamtehneto(arHleI m Angumloamre nitqnuu ma nmteucmh a(n8i7cis
Permut(a1t1)i ons Solevxeadm pilqneu sa nmteucmh a(n8i9c)s
Comn abti(i 1 o)1n s Hermiotpiear(na1 t0o6r)s
Prob(a1b2i)l ity Impo.rtthaenootrf qe umasnm teucmh a(n1i0c7s)
Othmeart hemraetlia(ct1ai4lo} n s Reviqeuwe satinpo�rn osb (l1e0m9s)
Vect(o1r4s)
Matr(i1c5e)s 2.QUANTUMME dlANicAsd-v1A1N.H d
Determ(i1n6a)n ts ropiAcNsd A roMiScp £cIT R1l1A- 7l2 1
Compnluemxb (e1rs7 ) Soluottfih Soecn h roedqiunagfteomionrru lti-electron
Ser(i1e7s) ato(m1s1 1)
Stiarplpirnogx (i1m7a)t,i on 1.T ime-indpeeprtuernt)dtaetJ_tnei(toOA1 r 1y·1 )
Evaluoaif\n itoe(ng1 r1!:fa ls Non:degpeenretruattioorbt,aeyt( i1o1n2 )
MemoraPbhiylsiiaco matilemali{ca1 9) Appliocfta htfeii orns petr-tourrdtbehareti oorny
helaitu(om1m 1 5)
L MEchANWiAcVsEM- £1c l1ANicAI Degenpeerrattuetr hbea(ot1ryi1 o7n)
·S taerfkfo entc htfe i erxsdtst teadot hfey drogeir
TR ETAM ENolfS iMpSlyErsE M·S 211-10
atom(119)
Elecatnrtdoh Onel Q du antum( 2T1h)e ory
2.T hvea rimaetti(ho1on2d 0 )
Ruthesrcfaottredr ing( 2e3x)p erimentAsp plioctfah vteai roinma ettihtooohnd e liautmo m
Rutheartfoommroiddc( e 2l3 ) (121)
Quantthuemoo frry a di(a2t4i)o n ThHea rtarnetdeh H ea rtrees-eFlocfk- consistent
Photoele(c2t4r)i c effect f1(eSlCdF )m(e1t2h8o)d
Bohtrh eoohfr yyd rog(e2n6 )a tom Sladteetre rfmoinrn· aenltae tcot(mr1so2 n9 )
Bohr atnhtdeh ooerr ioygf ithnMy drsopgeecnt rumT hSec hroedqiunagfteoairfir o n npi otte ebnatriraile r:
(28) Quanmteucmh atnuincna(el1l 3l2i)n g
Sommfeeerlxdt eonfts hiBeoo nht rh e(o3r1y) Simhpalrem oosnciic:l T lhaeat logre mbertahiocd
Alternativfeo trhe eexm pilsasonifaf otinin oen ( 137)
hydrsopgeecn(t 3r2u)m Angumloamre ntopuemr aetiogresn,l !mctions,
Duaclh aroafec lteec(rt3 r3o)n eigenvcaolmumaeutsti,ro e(l1a tainoldna sd.d er
de Brogeqluiaet('i33so} n oper(a1t4o1r)$
ThDea vissone-xGpeerr(mi3em5re) n t Derivoaftt hvieao rni ation theorem {148)
Heiseunnbf�!lgr ptraiinn(ct3i6yp) l e Atosmtiacat netdse srymm bols (149)
Competfocf(nte3 6) Thtee srymm bfootlrhsp 2e c onfi(g1su orJa tion
.
ii
Atomic spectra (154) Representations of molecular point groups (251)
A. . Fine struct4re 155) . ·~ .. Great orthogon'!lity theorem (G.O.T.) (253)
s.
Zeeman ·eff~ct (159) .. Important properties of irreps (253)
C. Stark effect (162) Use of G.O.T. to construct character tables for
The Thomas-Fermi model of the atom (163) molecular point groups (254)
Angular momentum revisited (165) Character tables for point groups (255)
1. Angular momentum matrices (165) Crystallographic symmetry (261)
2. Spin angular momentum and the Pauli spin Crystal Systems (262)
matrices (167) Molecular symmetry and crystallographic
3. Spin vectors for the spin·!-a system (168) symmetry (265)
4. Addition of angular momenta (169) Quasicrystals (265)
Review Questions (171) Problems (265)
:S _ ChEMicAl BoNdiNG : Mol1:culAR 5. GRoup lliEORY PART II : ApplicATioNs
OuANTUM MECHANics 177-246 267-J()l
Molecular orbital theory. -(MOT) (174) 1. Decomposing a reducible repre;entatioa into its
Term symbols for a diatomic molecule (184) irreducible representations (267)
Symmetry of molecular orbitals (185) 2. Group theory and normal modes of vibrations of
MOs for homonuclear diatomic molecules {186) • polyatomic molecules (268)
Molecular orbital energy level diagrams for 3. Procedure for determining the irreducible
heteronuclear diatomic molecules (188) representations of the vibrational modes in
nonlinear molecules (270)
Valence bond theory (VBT) (192)
Hybridization (f97) a. Nonnal modes of vibration of H20 molecule (270)
Calculation of the coefficients of AOs used in b. Normal modes of vibraiton of NH3 molecule (272) ..
hybridization (200) c. Normal modes of vibration of BF3 molecule (273)
Conjugated molecules (204) 4. Direct products of irreducible representations
(275)
HOckel molecular orbital theory of conjugated
systems (205) 5. Selection rules for atomic spectra (278)
Huckel's 4n+2 rule.of aromaticity-{210) 6. Use of group theory in determining the selection
. Wa1sh diagrams (225) . mies for the n -; ,r' and " .... lt. iransitions in
· form<;1.ldehyde (2791 ·
Born-Oppenheimer Approximation (228)
7. Use of. group theory in constructing hybrid orbitals
Hellmann-Feynman the(Jrm (229)
in simple molecules (282)
Computational quantum chemistry (232)
8. Use of group theory in factoring the secular
. A. Hartree·Fock·Roothaan self-consistent-field equation in MOT (285) ·
(SCFJ method for polyatomic molecules (234)
Trans 1.3-Butadiene, (285)
The Pariser-Parr-Pople approximaiton (235)
Benzene (289)
Configuration interaction (236)
9. Use of projection operators to determine SALCs
B. Semi-empirical and ab initio methods (236)
. ~~
Extended HOckel theory (EHT) (236) Miscellaneous seilved examples (294)
Semi-empirical SCF theory (238) Prob ms (301)
C. Density-functional theory (DFT) (239)
Time-dependent perturbation theory (TDPT) oleculAR SpEcrnescopy }02-J~2
(2
What is spectroscopy ? (302)
Review Questions (246)
Basic features of spectrometers (302)
~tiy_of.. sp_ei:lr.a!Jines (304)
4_. . Si,fioup· TkEORY PART I : BAsiC CONCEPTS
~s!..(305)
'', / 247-266
Rotational (microwave) spectra of diatomic
Symmetry elements and symmetry operations rti~J307)
(247) Relative intensities of rotational spectral lines (311)
Group postulates (249) Applications of Microwave spectroscqpy (312)
Types of groups (249) ~~pectra of polyatomic molec!Jles (313)
Other definitions (250) Stark effect in microwave spectra (314)
Point groups (250) ~er a~plications of microwave spectra (314)
<•a··-··--··~-·"'·-··---,.·-" M_.,.
iii .
Vibrational spectra of diatomic molecules (315) Study of hindered rotaticn by NMR spBd:oscopy
Rotafio~pectraof diatomic molecules (373)
• •..• ,;. • ,,,,~ (319)· Nuclear magnetic-double resonance.(371\}
Vibrational spectra of p<.:lyat~olecules Special topics in nuclear magnetic resonance (375)
---·~--······---······ (320}
1. Quantum mechanical description of the NMR
Rotation-vibrati~i:!.-~P~£tf!i~OJ 1101iato!llic molecules spectrum of an AB spin system (375)
------· .. .. . . (324)
2. Two-dimensional NMR spectroscopy (380)
Vibrational frequencies of different functional groups
3. NMR spectra of solids (380)
········----- (324)
4. Double resonance (381)
Raman spectrosc..QPy (326)
Quantum theory of Raman scattering (326) 5. The nuclear Overhauser effect (NOE) (381)
Classical theory offl~an sca.tteJiag (327) 6. Off-resonance proton decoupling (382)
Rotational Raman spectrum of a diatomic molecule - 7. Applications of 2D NMR (382)'
-- ... ----·· --~·------· (328) 8. Internuclear double resonance (INDOR) (385)
Rotation-vibration Raman spectrum (329) 9. Simplification of complex NMR spectra (385)
Experimental R~troscopy (3~9) 10. NMR of paramag.netic_compounds (387) .
__;wsc§nce~~~copy (331). 11. Chemically induced dynamic nuclear polarization
Laser RamaD.S.P.&.W.P.scopy (332) (CIDNP) (388)
· spectra (335) 12. NMR of liquid crystals (389)
'Franck·Co~d~~.J?![Q!i.!PJ.e (335) Magnetic Resonance Imaging {MRI) (390)
Ele,£!rgnic spectra .of.palyateffiic molecules (337) Electron spin resonance (ESR) spectra (392)
Charge transfe.r ~R~!@.(340) ESR spectrum of an unpaired electron (392)
Electronic of transition metal complexes Hyperfine structure in ESR spectra (393)
(341)
g-factor (396)
Energy level diagram for an octahedra(.!_r_ansition
Applications of ESR spectra (397)
metal complex ion (342)
ESR of anisotropic systems (399)
JaJ,n:TeUer distortion (343)
1. g-factor and hyperfine splittings (399)
Meiai-metal transiti~~s td-d bands) (343)
Change·traos.ieiiauds· (344) 2. Kramers' degeneracy and ZFS (401)
3. ESR of Transition metal complexes (402)
Electro~ic spectra of lanthaAides and actinides (345)
4. Multiple resonance techniques in ESR (406)
Electronic spectra of con]ugate<1.moi~9;1;~ (345)
SJ')in Hamiltonian (410)
Miscellaneous solved examples in spectroscopy
" .. . . . . (347) Mossbauer spectroscopy (412)
· Basic principle of NRF (412)
Review Questions and Problems (350)
Mossbauer experiment (414)
l .. /MolcculAR SpECrnoscopy II (NMR, ESR, ·More about Mossbauer spectroscopy (414)
NQR NRI: ANd PES) · n7-410 1. Chemical isomer shift (414)
2. . Nuclear quadrupole splitting (414)
Magnetic resonance spectroscopy (353)
3. Nuclear Zeeman splitting (415)
NMR speciroscopy (353) ·
Photoelectron spectroscopy (PES) (416)
NMR of a bare proton (355) Nuclear quadrupole resonance (NOR) spectroscopy ·
Experimental technique of NMR spectroscopy (357) (420)
Chemical shift (358) Zeeman effect in NOR spectra (425)
Shielding mechanism in NMR (360) Townes-Dailey theory of NOR coupling (426)
Nuclear spin-spin interaction : Fine structure in NMR Applications of NQR spectroscopy (427)
(362) Review Questions and Problems (429)
Chemical shift-equivalent and magnetically equivalent
nuclei (364) 3. Ekcrnic ANd MAGNHiC PRopERTi(S of
Mechanism of nuclear spin-spin interaction (367) Mol1:cul1:s 471-449
Complex NMR spectra (369) Electric properties of molecules (431)
NMR spectra of other nuclei (369) Polarization of a molecule in an electric field (431)
Fourier-Trans form NMR spectroscopy (370) Clausius-Mosotti equation (432)
Re!axatiqn processes in magnetic resonance (371) Debye equation (433)
Dependence of polarizability on frequency (436)
r
iv
Bond moments (440) Second virial coefficient {488)
Dipole moments and molecular structure {44'!1) Critical phenomena (489)
Group moments (441) .· . The F?.-V isolhslrms of carbon dioxide (490)
Magnetic properties of molecules (442) van der Waals eiiuation and critical sfafe
Molecular interpretation of diamagnellsm lill'Ai (491)
paramagnetism (444) law (principle) of corresponding states (493)
Measurement of magnetic suscepti!Jffity f447) Molar mass and density of a real gas (495)
Ferromagnetism and antiferromagnetrsm (414'8) liquefaction of gases (495)
Review Questions and Problems (449) Production ot low temperatures by adiabatic
demagnetization (496)
9. fl.U: GASEOUS STATE PART I : ld£AI GASES Review Questions and Problems (498)
450-478
I I. TltE LiQuid STATE : PliyslcAI PRopERTiES of
Kinetic molecular theory of gases (450)
LiQuids 499-5 15
Pressure of an ideal gas (450)
Gaseous, liquid and solid states (499)
Derivation of the gas laws (451)
Vacancy theory of liquids (499)
Ideal gas equation (452) of
Free volum~ a liquid (500)°
Kinetic energy and temperature (453)
Physical properties of liquids (500)
Maxwell distribution of molecular ~elocities (4541)
Vapour pressure (500)
Maxwell distribution of molecular ,1nergies (45SJ
Surface tension (502)
Types of molecular velocities (4 56) • Kelvin equation for vapour pressure of a
Derivation of expressions for molecular velocities droplet (506) .
(4.&7) Excess pressure in a drop (506)
Expansivity and compressibility (450) ·Laplace equation and the Young-Laplace
Collision parameters (461) equation (507)
Collision diameter.(461) Surface active agents (507)
Collision cross-section (461) Viscosity (508)
Collision number (461) Effect of temperature on viscosity (509)
Reynolds number (509)
Collision frequency (462.J
Refraction (510)
Mean free path ( 462)
Optical activity (511)
Transport properties (463)
ORO and CD (512)
Thermal conductivity (465)
Structure of liquids (512)
Viscosity (467)
Review Questions and problems (514)
Diffusion (470)
Summary of transport properties in a Q!!S (471)
1. 2. liQuid CRysrAls · The _MESO_MORpkic STATE
Degrees of freedom of a gaseous molecule .
. 516-~24
(472)
The principle of equipartition of energy (474) Liquid crystals (516)
Contributions to heat capacity of an idea! gas (475) Vapour pressure-temperature diagrams (517)
The Barometric formula (477) Thermography (518)
LCDs and the seven segment cell (518)
Revies Questions and Problems (478).
Classification of Thermotropic liquid crystals (520)
Smectic liquid ,crystals {520)
10. THE GASEOUS STATE PART II : REAi GAS{",; Nematic liquid crystals (521 J
479-496
Cholesteric liquid crystals (521)
Deviations of real gases from ideal behaviour (479)
Disc shaped liquid crystals (522)
Explanation of the deviations (480)
Polymer liquid crystals (522)
Equations of state for real gases (481 J
Polymorphism in thermotropic liquid crysla/6 (522)
van der Waals equation of state (481}
Pressure-induced mesomorphism (523)
Other equations of state (484)
Molecular arrangements in various states of liquid
Virial equation of state (486)
crystals (524)
Intermolecular forces (487)
Review Questions (524)
Lennard-Jones (6-12) potential (488}
v
1} :_ THE FiRsT LAw of TlirnModYNAMics App:;cations of bond energies (568)
525-551 Review Questions and Problems (569)
Importance. of thermodynamics {525)
Limitations of thermodynamics {525i
I 5. Tl1E SEcoNd LAW of fl.1rnModYNAMics
Some basic terms used in lhermodymmits (525)
Hl-608
Thermodynamic equilibrium (526}
Limitations of the first law : Need for tt.e second
Extensive and intensive properties (521)
law (571)
Thermodynamic processes (527)
Spontaneous er irreversible processes (571)
Nc1ture of work and heat {528) Cyclic process (572)
The first law of thermodynamics {528) Carnot cycle (572)
Internal energy (529) The second law of thermodynamics (574)
State functions, exact and inexact differentials (530) Carnot theorem (574)
Euler reciprocal relation (531) Concept of entropy (575)
The cyclic rule (532) Entropy change in an isothermal expansion of. an
Enth?lpy (533) . ideal gas (577)
Heat capacity (534) Entropy changes in reversible aJ'ld irreversible
Relation between Cp and Cv (5~5) processes (577) ·
Expansion· of an ideal gas anct changes in Entropy changes accompanying changes of phase
thermodynamic properties (535) (578)
A Isothermal expansion (535) Calculation of entropy changes of an ideal gas
B. Adiabatic expansion (538) with change in P, Vand T(580)
Entropy of mixing of ideal gases (582)
Final temperatures in reversible and ineverslble
adiabatic expansions (538) Standard entropies (583)
Comparison of isothermal and adiabatic Physical significance of entropy (584)
expansions (542) Work and free energy functions (584)
Reversible isothermal expansion of a real gas (543) Variation of free energy with T and P (586)
Joule-Thomson effect (545) Maxwell's relations (586)
~oule-Thomson coefficient in an ideal gas (546) Criteria for reversible and irreversible proc.;sses
jouie-Thomson coefficient in a real gas (547) (589)
Zeroeth law of thermodynamics j5{9'} · : Gibbs-Helmholtz equation (590)
Absolute temperature scale (549) Thermodynamics of open systems : Partial molar
properties (591)
Review Questions and Problems (550)
Chemical potential (592)
Gibbs-Duhem equation (592)
14:)1-rrnMOchEMiSTRY . 552-570 · Variation of chemical potential with temperature (593)
Variation of chemical potential with pressure (593)
/ Change of internal energy in a chemical reaction
(552) Chemical potential in a system of ideal gases (593)
Change of enthalpy in a chemical reaction (552) Determination of partial molar quantiiies (595)
Exothermic and endothermic reactions (552) Clapeyron equation (597)
Clapeyron-Clausius equation (598)
Relation between heats of reaction at constant
volume and at constant pressure (553) Applications of the Clapeyron-Clausius equation
(600)
Standard enthalpy changes of reaction3 (555)
Fugacity and activity (601)
Determination of enthalpies of reactions (558)
Determination of fugacity of a gas (602)
Variation of enthalpy of a reaction with temperature:
The Kirchhoff equation (560) Fugacity of a gas in a gaseous mixture (005)
Flame and explosion temperatures (562) Fugacity of a liquid component in a solution (605)
Hess's law of constant heat summation (563) Concept of activity (605)
Applications of Hess's law (564) Activity coefficient (606)
Standard states (606)
Measuring the enthalpy of combustion (565)
Bond energies (567) Review Questions and Problems (60n