CRM DEPARTMENT OF CHEMISTRY FACULTY OF SCIENCE “ABUBAKAR TAFAWA BALEWA UNIVERSITY, BAUCHI CHM 111- GENERAL CHEMISTRY | LECTURE NOTE 2019/2020 “for STUDENTS FROM FACULTIES OF SCIENCE ENGINEERING AND ENGINEERING TECHNOLOGY ENVIRONMENTAL TECHNOLOGY AGRiC AND AGRIC TECHNOLOGY MEDICAL SCIENCE Course lecturers; U:f Hassan, 0.£.A Boryo, R.S‘Oguike, H. Akarinang, N.M Lawal, U.I Tafida, K.M Yahuza, A.U Baramty, U. Bello, A:A Abubakar, M.|ji, R.M Baba Owmet SThis lecture note is segmented into five sections; section 1- Kinetic theory and general chemistry of gases/liquids section 2- Characteristics of solids and phase equilibria section 3- Chemical and ionic equilibria Section 4- General thermodynamics and thermochemistry Section 5- introduction to chemical kineticsINTRODUCTION tends to introduce stusdents to the chemistry of yases This part of the course GASES IDEAL GASES An Ideal Gas.is any gas whose pressure P, volume V, and temperature T are related by the ideal gas lawiequation of state. PV = nT where n is the number of moles of the gas, R is the ideal gas constant. DERIVATION OF IDEAL GAS EQUATION ‘The ideal gas equation is derived by combining Boyle's law, Charles’ law and Avogadro's law Boyles Law + Charles Law +Avogadros Law = Ideal Gas Equation C Boyle’s Law Volume is inversely proportional 1 pressuré at constant temperature and 2 fixed amount of gas Va 3 (T,nconstant) (i) O Charles’ Law Volume is directly proportional to absolute temperature at constant pressure and a fixed amount ofgas. V aT (P,nconstant) i) O Avogadro’s Law Volume is directly proportional to the amount of gas at constant pressure and temperature Van (P, T constant) Gii) eral gas law: These three laws.can be combined into a single more g: F (vs Equation (4) is called the Universal Gas Law. It is also called Ideal Gas Law it applies to all : ideal behaviour i.¢., Obeys the gas laws perfectly, The deal Gas Law inay rectly proportional: to the number of gases which exhibi be,stated as: “the; yolume ofa. given: amount of gas is: moles of gas, directly proportional to the absolute temperature, and inversely proportional. to the Introdiicing the proportionality. ccnstant R (called, the Gas constant) in equiation (iv), pressure” we can write ar Y= R= OR PV = nRT ™)This part of the course intends to intwoduce stuslents to the chemistry of gases GASES IDEAL GASES An Ideal Gas-is any gas whose pressure P, volume V, and temperature T are related by the idea! gaslaw/equation of stale PV = nRT where n is the number of moles of the gas, R is the ideal gas constant. DERIVATION OF IDEAL GAS EQUATION The ideal gas equation is derived by combining Boyle's law, Charles’ law and Avogadro’s law Boyles Law + Charles Law +Avogadros Law = Ideal Gas Equation CG Boyle's Law Volume is inversely proportional to pressure at constant temperature and a fixed amount of eas. Ya2(T,nconstant) (i) Charles? Law Volume is directly proportional to absolute temperature at constant pressure and a fixed amount ofess. V @T (P, nconstant) (i) 2 Avogadro's Law Volume is directly proportional to the amount of gas at constant pressure and temperature Van (P,T constane) (iii) These three Jaws can be combined into 2 single more general. gas law: vem one ivy Equation (4) is.called the Universal Gas Lav. Iti also called Ideal Gas Law it applies to all gases which exhjbit-ideal behaviour i.e., obeys the gas laws-perfectly, The Ideal Gas Law may be stated as: “the. yolume of.a. given. amount. of gas is:directly proportional: to the number of” moles of ga’, direcily proportional to the absoluie temperature, and inversely proportional to the pressure”. Introdicing the proportionality constant R (called, the Gas constant) in equation (iv), we can write . v=R™ OR PY = nRT )ion ($) 18 called the Ideal Gas Equation, It is also cauied an Equation of State for a gas decause it contains all the variables (T. P, V and n) which deseribe completely the condition or state of any gas sample. If we know the three of these variables. it is enough to specify the system completely because the fourth variable can be calculated from the ideal-gas equation The Numerical value of R: : ” 1m the ideal-gas equation, we can write Cae 8 = FWe know that one mole ofiany gas at STP occupies a volume of 22.Alitres. Substituting the values in the above expression, we have prs atm X 22.4dm? Tmole X 273K Other values of R include © 8.314SJmor'k" + 62.364Torr dm3mol'K"" + note: 8.3145Jmol"K" is the'SI unit for the gas constant 0.0821atmdm?mol7? 7? Hints: 0 Because of the various value of If one can use to solve a problem, it is crucial to match your units of pressure, volume, number of mole, and temperature with units of R. O If you use the first value of R, which is 0.0821atm dm3mo!"'K’', your unit for Pressure must be atm, for Volume must be litre, for Temperature must be Kelvin. G If you use the second value of R,, which is 62.364Torr dm3mol"'K"', your unit for pressure must be torr, for volume must be litre, for Temperature must be Kelvin, CALCULATING THE NUMBER (OF MOLES, n Number of moles = 1 Molar Mass O Example: 1 * 153 Calculate the nuniber of moles of the! following gases; ~ mo (1) 5.6g of Nitrogen gas, Na(g) (2)1.32g of COx(g) Solution: iv (1) nNa(@) = (5.6/28)mol = @.20mo} (2) n CO2x(g) = (1.32/44)mo: = 0.03mol ‘The usefulness of the ideal gas equation is that il relates the fovr variables, P,V,n and T, that describe a sample of gas at one set of conditions.(O Fyample: 2 What pressive, in atmosphere is exerted by 54.%¢ of Xe ana line flask at 293K? (Xe = Vmol, T= 293K and P=? ART for P and substituting gives ART /V = (0.41 1mol)( 0.0821 atm dm? molK(293K 1.9L; P = 9.89aim 0 Exampte: 3 $.0g of neon 1s at 256mmHg and at a temperature of 35°C. What is the volume? Solution: P= 256mmHg, m = 5.0g,.T = 35°C, R = 0.0821.atm dm mol 'i¢"', ¥ Convert as necessary: Pressure: 256mmHg * (Jatn/760mmilg) = 0.3368am Moles: 5.0g Ne * (1mol/20,1797g) = 0.25 snol Ne , Temperature: 35°C + 273 = 308K Plug in the variables into the appropriate equation V = (akT/P) (0.25mol)( 0.082 1atmdm? nol” 1K"")(308K) ae eee 0.3368atm =? O Example: 4 What is the gas’ temperature in Celsius when it has a volume of 25 dm3, 203mol, 143.Saim? Solution: P= 143.Saim, n= 203mol, V = 25 dm?, R = 0,U82!atm dm3mol"'K"!, T=? PV fui (443.Saem)(2Sdin £55 (203:n01)( 0.082 1atmdm3moi “Converting the temperate 19 Celsius, gives 215.4% - 273K = -57.4°C : = 215.4K. . EXPRESSING PV, = nRT INTERMS OF DENSITY, p Density is defined as mass per unit volume i.e., p = 1 /Y 0) For an ideal gas PY = nRT : Y = nkT/P : (ii) Put eqn (ii) in (i), we have P p= Po/nRTReese’ (iv) a = mM the Butn = mass/molar mass Pategn (iv) in (iii) (v) = PM/RT Okxample:5 sie i 1 Calculate the density of Ammonia (NH) in gL” at ©989atm and 35°C. ° s . & : s/s Solution: Fl] co P=0.989atm, T = 328K, R = 0.0821 aun dm3mol"'K" é ‘ The molar mass of NH; is 17.03gmo!" h #4 = PM/RT = (0,989aumy{ 17.03gmol") "(0.0821 am dmmolK"Y328K); a‘, 4 ° p=0.625gL’ {3 z 0 Example: 6 gf 4 & ! What isthe density of nitrogen gas (Nz) at 248.0 Voir and 18°C. + Bf { g og!) ae Solution: Ve SX P =248,0Torr, R = 0.0821 amLmol''K"', = 18°C, V=2,n=7 {ff 2 So & ef Convert as necessary: (248Torr) X 2" = 0.3263a0m ete x/2 i a 4 “oF é | 3} 18°C + 273 = 291K Shot eK Using the equation, p = PM/RT, gives % 14.01 gl * _ (0.3263aem)(2 gmt” ) _ spaeyt (QIK) * (@0821atmLmot DALTON?S LAW OF PARTIAL PRESSURE It states that! the total pressure of a mixture of gases is equal to the sum of the partial pressures of all gases present, Matiematically the law can be expressed as: Ptotal =P; + Pot Py. coset it Py : Gy here Pi,'P2 a re pattial piéssures of the three gases'I, 2 arid 3; and so.on. Dalton"'s Law of paitial pressures, followed by application of the ideal-gas equation PY = naT sepajately to exch gos of the mixture Thus we can write she partial pressures P1, Pz and P5 of the ne m(B), a= m(B) a= mE) 3. a7 total pre ai of the mixture is ie moles of yases 1.2 ay Where m1, m2 and= he Crea \s a A Me ie on Nae if number of me! of Hed =< 64g. 355 “ mol of HCL 101) _ 955 ve ff %ner (warez HCL + mor of | za) = (saps) = 923 I Eye AS te ie RELATIONSHIP BETWEEN PARTIAJ. PRESSURE, MOLE FRACTION AND TOTAL, PRESSURE Consider an ideal gas mixture (binary) of A and B. From the ideal gas equation PY = nT: Py = n4RT/V; i Prat = Moa RT/V. Divide eqn (i) by eqn'(i Pa! Paoat “Mal Mein = Xa - +: Pa= Xa Prout = . : v The partial pressure of a particular component is equal to its mole fraction multiplied iy the .otel pressure. 0 Example: 10 A mixture of gases contains 2.1’ moles Of Argon (Ar} and 1.6 moles of Xenon (Xe). Calculate the partial pressures of the gases if the total pressure is 2.08 atm. Solution: Firstly, Calculating the mole fraction ‘The partial pressutewill be’ * « Pye = XyePr = 0.822 « 2.0Uaem = 0.864atm "Py = x4pPy = 0.867 = 2.00a¢m = 1.234atmx KINETIC MOLECULAR THEORY a Maywell and Boltzmann (1859) developed’ me 's and the gas laws. It is based on tne furdsmentai concept that a gas is made of a large sumber of molecules in perpetual motion This theory is called the Kinetic Molecular Theory the behaviour of myntical theery’ to exp or the Kinetic Theory of Gases, Assumptions of theKMT i 1) A gas consists of extremely small discrete pa:ticles called molecules dispersed throughout the somtainer, It means that the actual volume of sie molecules is negligible compared to the total volume of the gas. The molecules of a given gas are identical and have the same mass (in), 2) Gas molecules are in constant random motion-with high velocities. They move in straight lines ‘with uniform velocity and change direction on collisivn with ather molecules or the walls of tise container, 3) The distance between the molecules is very Inzge and it is assumed that van der Waals attractive forces between them do not exist. Thus the gas molecules can move freely, independent of each other. : 4) All collisions are perfectly elastic. Hence, there is during collision. 5) The pressure of a gas is caused by the hits recorded by molecnes on the walls of the container. < ©) The average kinetic energy (mv?) of the gas molecules is directly proportional to absoluie temperature, This implies that the average kinetic energy of molecules is the same at a given temperature. no loss o¥'the kinetic energy of a molecuie FUNDAMENTAL EQUATION FOR THE PRESSURE OF A GAS. 1 Py ym un This is the fundamental equation of the kinetic melecular theory of gases. It is called the Kinetic Gas Equation. Thisequation although desived for a cubical vessel, is equally valid for a vesse! of any shape. The available volume in the vessel couis! well be considered as made up of alarge number of infinitesimally small cubes tor each cf which the'equation holds. vuvis the mean of the squares‘of the individual velocitie’ of all the N molecules of the gas. OKINETIC GAS EQUATION INTERMS OF KINETIC ENERGY 7 “i LeiN be the number of molecuies in a given mas. sf gr: PY = daNu?..... 2 2+ muiNee fe Mvlecuie. where + average kinenic energy of a si 4 Therefore, wh re E is the ioral kinetic energy of all the N sion (4) is called the cules, Eq Kinetic gas equation in terms of kinetic energy. We know that the general ideal gas equation is PV = RT. From (4) and (5) above SErorT.... 6 For one mole of a gas, the kinetic energy of N inivlzcuies is, palit aa ? O Example: 11 Célculate the kinetic energy of two moles of Nz at 27°C. Take R = 8.314)K"'mol" Solution: We know E =2 nT, where n = 2.0mol, T= (27 +273) K'= 300K ad R= 8.314)1C"'mol! on substitution we have E =2 * 2.0mol * 8, Km! * 300K =7482.6) Therefore the kitietic energy of two moles of Nz 15 7482.6). ‘ODEDUCTION OF GAS LAWS FROM THE KINETIC GAS EQUATION *) Boyle's Law! cording 1o.thé’Kinetic: Theory, tliere is a direct progortionality between absolute temperature and avérage kinetic energy of the molecules i “Be tain? = ter, mine? = Zkr . Substituting the above value in te kinetic.gas equation a PY = ZmNu? we have PV = ZiT, The product PV, therefore, wifl have a constant value constant temperature. This is Boyles Law.2) Charles Law: As derived above, PY = i Divide both sides of equation (2) by P, vsisST —— Atconstant Pressure, P V =k'T where k’ is also a constant Eqn (ii) is Charles’ law ‘This implies that, at constant Pressure, volume of a gas is prop: this is Charles Law. nal to Kelvin temperature and 3) Avogadro's Law: . Consider equal volume of 2 gases at the same pressure, Py = FM? ssessen(i) kinetic eqn of Ist gas Pv Therefore i pm aN att? Gi) kinetic eqn of 2nd gas iii) 1 2 2 3 Smt? = Sma Natty? cree When the temperature (T) of both the gases is the same, their mean kinetic energy per molecule will also be the same. Dividing (iii) by (iv), we have N=N2 Or, under the same conditions of Temperate and Pressure, equal volumes of the 2 gases contain the same, number of molecules This is Avogadro"s Law. 4) Graham's Law of Diffusion: Im, and'my are the masses and u, and up the velocities of the molecules of gases | and 2, then at the site, pressure and volume, L a sm Muy? = ZmNou,? .. N m muy? = Maz? If My and Mp represent the molecular masses of gases band 2, then,‘The rate of diffusion (r) is proportional to the velocity of molecules (1). therefore, rate of diffusion af gast_r,_ [i rate of diffusion of ges2 r, |M, This is Graham's ‘law of diffusion. : ROOT MEAN SQUARE VELOCITY TEV, Va, Va os squares of all the velocities is: . Vaare the velocities of n molecules in a gas, U?, the mean of the Vi2 +VQ? + V3" + n Taking the square root, we have, Vy? +? £V5t + : 7 Uis thus the Root Mean Square Velocity or RMS velocity. It 1s denoted by U. The value of the RMS. velocity U, ata given temperature car. be calculated from the kinetic gas equation, mNue yrs BY mw ForOne.nole of ideal gas, PV = RTtierefore U? = a ORU?= oo Where M = molat'mass. [ser a RMS‘ velocity is is Supetion.to the: average velocity considered earlier. With the help of U, the total Kinetic Energy ofa gas' sample can be calculated Rea Gas eA Distinetion between Taéal and Real gases : 1. An ideal gas is infinitely. compressible; teal gas will condecse 10a liquid at some pressure. 2. The panicles of arvideal gas lose,no energy to its evrtaine:. « real gas condticts and radiates heat, thereby losing energy. 3. There is no attraction between the molecuies oan ideal ga 4. An ideal gas can follow the formula PY = nR7 A real gas ‘eal gas has particle atactions. + not follow this formulapEVIATIONS FROM IDEAL BEBAVIO An weal gas is one Which obevs the gas laws or temperatures. However, no gas is ideal, Armost all gaves show § 1 ideal behavior. Thus the gases Na, No and CO: w-hicis fail to obey the ice termed non ideal or real gases. ous equenion PY as equation ae COMPRESSIBILITY FACTOR This is a quantity that measures the devi : Pim the equatior on Where Z = compression factor, Viq = : s jon of a real ges fron» ideal behaviours, It is defined by P, Rand T have their usval meanings. => Z= 1 at alll conditions, For a real gas, Z depends on the value of ?Vm relative to RT. At high pres. ures PVm > RT so that Z > 1. The gas is said to deviate positively from ideality and is less compressible than an idea! gas. Atlow pressure, P¥m CaO + COrey Number of phase = 3 This systein constitute of 2 solid phase, CaCOs and CaO and are gaseous phase, that of COz . . Ammoniiim chloride undergoes thermal decomposition the chemical reaction is: NH Cli —* NH) + HChay Number of phase Page | 22 So “4system has two 1 and HCI ‘A solution of NaCi in On solid, Nti Cl andl one gaseous, a mixture oF water Number of phase = } PHASE EQUILIBRIUM This is a balance between phases that is the co- existence of two or more phases in astate of dynamic equilibrium, tn other words, the Felative quantity or compositior n of each phase remains unchanged unless the external condition is altered, Examples of a phase tran. tion, below; Tenpertue 69 witann edubscrintartnanotOA aang MM edo ice ne AOHASE ey ‘ =. condi: 123 <~ afio the number of components COMPONENTS: The number of components ct'a systen: at equilivrium is a smallest number of undependently varying chemica! constituents using which the composition of each ad every phase in the system can be expressed, OR A component is a chemical species which may be used to specify the composition of a system. A system may have one or more components. It should be-noved that the term ‘constituents’ is different from “ components” which has a special definition. When no reaction is taking place in the system, the number of components is the same as the number - of components is the same as the number of constituents. For example, pure water is 2 one component system because all the different phase can be expressed i in terms of the single constituent water. PHASES AND COMPONENTS OF DIFFERENCES [sino Example Phase Number of Components | 1 Anice | A-solid phase [One water | block | only | . f2°.e 5 A bottle | Liquid and Ont’ “ol of vapour phase(a \ perfume i perfume: | smail amount of : i ' perfume vapour | | over liquid per) | 8 “A smal! 7 Soli! and fiquié” {Two ! amount { Page | 28und.ssolved i chloride ! found in |is added | solution) a | saturated | sodium | chloride ; solution Example Counting the number of component a. A mixture of ethanol and water is an example of a two compoient system We need both ethanol and water to express its composition, b. An example of a system in which a reaction occurs and equilibrium is established is the thermal decompositions of solid CaCo3. In this system, there are three distinct phases. Solid CaCoy, solid CaO and gascous Co, though there are 3 species present, the number of component is only two, because of the equilibrium = CACO => CaO + CO . “Any two.af the three constituent may be chosen as the component. If CaO and CQ) are chosen the compo: of the phase CaCO; is expressed as oné mole of component COz plus one mole of component CaO. Ifon the other hand CaCO;and CO were chosen, the composition of the phase CaO would be described as one mole of CaCOs minus one mole of CO2, PHASE RULE The phase so known as the gibbs 4 & PagePhase Rule. when a heisrogeneors System at equilibrium ata definite temperature and pressure, the number of de: es of freedom is equal to by 2 the difference in the nunber of components and the number of phases provided the equilibrium is not influenced by external factors such as gravity, electricity or magnetic forces surface tension esc Mathematically, the rule is written as F=C-P+2 Where: F= number of degrees of freedom : C= number of component P= number of phases of the system For understanding the various applications of phase rule a clear understanding of the various terms: phase (P), components(C) and degrees of freedom (F) present in the phase rule NOTE: phase(P) and components(C) explained above: Degrees of Freedom: The smallest number of indepersdently variable factors such as temperature, pressure and concentration which musé-be required in order to define! ithe system completely are called the degree of freedom, Degree offreedsm of & ‘system is also known as variance. at - When a system having no degree of freedom E=0 itis called non-vatiant system or invariant system - When a system having only one degree of freedom, = | itis called invariant or monovariant ~ A system having two degree of freedom 4+ sa Bavarian system e.te. Page jExample a The system ice water vapour ines no degree of treedom (ie F = 0). Because the three phases of water i.e ice, liquid water and vapour can together in equilibrium only at 2 particular-temperature and pressure (corresponding to the freezing point) and no factor is necessary t0:be specified to define the system. Hence, 2 system consisting of ice, water and vapour in equilibrium has no degree of freedom i.e is 2 non-varient or invariant system. Iceas wateray vapour) Number of phase = 3 Number of component = 1 F=C-P+2 F=1-3=2 F=2+2=0 Degree of freedom F = 0 2. Calculate the degree of freedom F of the following equation 2t equil CaCOx3 —* CaO + COry Solution There are also three different chemical constituents, but the number of components is only two because any two constituents completely define the system in equilibrium. Any third constituent may be determined if the: concentration of the other two is known. Number of phases (P) = 3 Number of compenent (C) = 2 F=C-P+2 F=2-3+2=1 — Page | 27