Properties Solutions Experiment II Partial Molal Volume The phase rule in general is written F = C — P + 2. Fora single pha and a single component, F = 1 —1+ 2 = 2. This means that in o to specify the state of a system consisting of one component and phase completely and unambiguously, a minimum of two properti the system must be given. These are usually pressure and temperat since it is experimentally convenient to control these variables. For extensive thermodynamic property Y (such as V, G, H, S, and A) can write, for a one-component system, Y=f(P,T) The total differential is oY oY av-(%) a+ (22) an Y=f(P,T,m,m) and the total differential becomes a= (ar) ar+ (Fr) aT oP Tiny ra or Pyny na +(F) dm +(5,) dm on, PT on, PT ny501 The partial molal Y is defined as = oY Y;= (5) (11-5) 9n; } p 1 At constant temperature and pressure, Equation 11-3 becomes Y =f(m, m) (11-6) and the total differential becomes Y oY dY= (5) dn + (sn) dn, (41-7) On2} or. 85 Jor which can be written more compactly as dY=Y,dn, + Y,dm (11-8) Of all the extensive thermodynamic properties, the volume is the easiest to visualize; this also holds true for the partial molar volume, defined as Vi= (on) (11-9) On; Pray so that Equation 11-8 can be written dV =V, dn, + Vz dm (11-10) The integrated form of this equation (Klotz, 1950) is V=nV, + mVr (41-11) which is an interesting and surprising result. Let us see why. Partial Molal Volume of Some Real Solutions What is so surprising about this rather innocuous-appearing equation? Well, if a solution is ideal, then its volume is just the sum of the volumes of the solute and solvent: V=anV3+mV3 (11-12) Benzene and toluene form an ideal solution. The volume of 1 mole pure benzene is 88.9 ml; the volume of 1 mole pure toluene is 106.4 ml. Equation | 1-12 states that 88.9 ml benzene mixed with 106.4 ml toluene results in 88.9 ml + 106.4 ml, or 195.3 ml of solution. Common sense suggests that the volumes add up, since the volumes of substances in solution are extensive properties. On the other hand, water and ethanol do not form an ideal solution. The volume of 1 mole pure ethanol is 58.0 ml and the volume of 1 mole pure water is 18.0 ml. However, 1 mole water mixed with 1 mole ethanol does not result in 58.0 ml + 18.0 ml, or 76.0 ml, but rather 74.3 ml!Experit According to Equation 11-11, it is the partial molal volumes th additive or extensive properties. When the mole fraction is 0.5, the p; molal volume of ethanol is 57.4 ml and the partial molal volume of wate is 16.9 ml. With Equation 11-11, we can now calculate the volume g the solution: 2 1 mole X 57.4 ml/mol + | mole X 16.9 ml/mol = 74.3 ml (aL * which is exactly what is observed. Note that the values just cited for partial molal volumes of ethanol and water are only for a partic concentration; in this case, the mole fraction equals 0.5 and applies‘ to the water-ethanol system. Apparent Molal Volume The experimental determination of partial molal volumes is, in princip quite simple and involves the careful measurement of the densities solutions of known concentrations. The calculation is simplified by use of a related quantity, the apparent molal volume of the solute, ¢ Consider the volume of a solution as 7, moles of a solute are added fixed , moles of solvent. The volume of the solution might change shown in Figure 11-1. The volume due to the added solute (per mol is called the apparent molal volume $V. Figure 11-1 shows that op (Vv Slope at 7, V,= = b 2 (ann moles of solute Volume due to added solute = 7, 6V Volume Volume due to = n, moles of solvent = 1,77 Moles of solute Figure 11-1 How the total volume of a solution V depends on the volume of the pur solvent and the apparent molal volume of the solute ov.ch » 503 V sotution — Veotvent y= Vsotution en 14 $ moles of solute ( ) or vom 11-15 th ( ) eV Thus, in Figure 11-1, the volume V of the solution at any particular added m moles of solute is given by a rearrangement of Equation 11-15: V=n Vo + moV (11-16) It should be clear from an examination of Figure 11-1 that it does not make sense to define an apparent mola! volume for the solvent, since the number of moles of both solvent and solute cannot be held constant simultaneously. Partial and Apparent Mola! Volumes from Density \Measurements The Solute. The apparent molal volume is useful because it can be measured easily (as Fig. 11-1 suggests) and because the partial molal volumes of both the solute and solvent can be calculated from measure- ments of the apparent molal volumes. Relating the partial molal volume of the solute to the apparent molal volume is straightforward: partial differentiation of Equation 11-16 with respect to m2 at constant ”% gives R= (5) = oV+ mS} (11-17) Next we wish to relate the apparent molal volume to the usual ex- perimental parameters, namely the molality m and the density d of the solution. Equation 11-15 defines apparent molal volume. The volume V of solution can be expressed as _ Wt. solvent + Wt. solute d _ nM, + mM, _ 1000 + mM, ~ d d Vv (11-18) where M, and M, are the molecular weights of the solvent and solute, respectively. The term 7, V9 in Equation 11-15 is just the volume of the solvent; when the concentration is expressed in molality, the mass of solvent is 1000 g, so the volume of the solvent is nV = 1000/d, (11-19)Exper Substitution of Vand nm V? from Equations 11-18 and 11-19 into Equa tion 11-15 gives us our working equation for experimentally measu; oV, the apparent molal volume, with n equal to m: i ov = L ae + mM _ ad m d da, a where d is the density of the solution and d, is the density of the sok One last point: we should substitute m for n, on the right sic Equation 11-17, and then make the following substitution, since ¢: a linear function of Vm, but not of m (Lewis and Randall, 1961): (#*) - (24m) (2) _3 (#2) am}, \aVm),,\ am },, 2Ve\AVne ‘ When Equation 11-21 is combined with Equation 1 1-17, we obtait working equation for V2: n= (0B) On The Solvent. In order to calculate V;, let us first rewrite Equat 11-11 as : - V- mV = nm Substitution of the right sides of Equations 11-16 and 41-17 for V Vp, respectively, results in - Vv 1 = agV. om}, Ona | ny Since we wish to use molality for concentration, 7) = mand 1 = 5 The volume of | mole of solvent V9 equals M,/d). When these val and the right side of Equation 11-21 are substituted into Equati \ 11-24, the result is our working equation for V;: 7, -(% ~My mi? (36¥ 1" Van}, 4 111.02 avm!},, SAFETY CONSIDERATIONS None. a : ; F Apparatus In addition to sodium chloride, the experiment requires two pycnometer of the Ostwald-Sprengel (Fig. 11-2) or Weld type with a volume of 4a i505 Fiducial marks Figure 11-2 Ostwaid-Sprengel pycnometer. to 50 ml; five 100-m] volumetric flasks; a rubber bulb for filling the Ost- wald-Sprengel pycnometer; and clean, dry cotton cloths or tissue paper to wipe the pycnometers dry. . EXPERIMENTAL PROCEDURE a Prepare about 100 ml of five solutions of sodium chloride in distilled water ranging in molal concentration from about 0.3 to 3.0. Weigh the solute and solvent with an analytical balance into dry glass- stoppered flasks. The densities of the solutions are measured with an Ostwald- Sprengel pycnometer that has been calibrated by calculating its vol- ume from the mass of water it contains and the density of water (Table 14-2, Chapter 14) at the temperature of the measurement. First, rinse the pycnometer with a few portions of distilled water, followed with a few milliliters of acetone. Fill the pycnometer by dipping one arm into the liquid and pulling the liquid into the vessel with a rubber suction bulb attached to the other arm. With an as- pirator, suck air through it to remove most of the acetone and then dry at about 110°C for 10 to 15 minutes. Let the pycnometer hang in the balance room for 30 minutes before determining the weight of the empty, dry pycnometer. Exercise extreme care in weighing, filling, rinsing, cleaning, - handling, and drying the pycnometer. After the pycnometer is clean, do not touch it with your fingers. Allow it to equilibrate with the humidity and temperature of the balance room for the same time period before each weighing. , After weighing the empty pycnometer, fill it with distilled water and hang it in a 25°C thermostat bath. Be sure that no air bubblesProgram Apparent; uses crt? 58.443; (* formula weight of Nacl *) 0.99707; (* density of water at 25 deg C *) nl 55.513 (* moles of water in 10009 water *) ArrayLength = 207 (* maximum number of data pairs *) Type Ary = Array (1. -ArrayLength] of Real; Var m,d: Ary? (* lists of input data; molalities & densities *) N: Integer; (* requested number of data pairs *) a const M2 dal nul Cannan ERR RA ARE ARERR A RIERA RRA RESETS SS Function Phi (m,d: real): Real; (* Phi is apparent molal volume *) var V, Vsol: reali (* Vv is volume of solution *) (* Vsol is volume of 1000g of water *) (1000 + m*M2) /d? (* volume of solution *) 1000/dal; (* volume of solvent *) (Vv - Vsol)/m (* apparent molal volume *) End; (* Phi *) ConA REE ARERR REE) procedure GetData; var I, X,Y: Integer? (* Screen Coordinates *) Begin CLRSCR? Write ("How many molality-density pairs do you wish to input? ' eReadln(N) i Write('Please enter ', Ne1,' molality-density pairs: ')? Writeln; : For I:= 1 to N do Begin Write('molality # ,:1,': ')F X:= WhereX; ¥:= WhereY; Read(m{I)}); GoToXY (X+10,Y¥)# . Write(' density # ',I:1,': "ye . Readln(da[1I]); End; (* For *) Writeln; End; (* GetData *) CoE A EE ERROR OR PIERS ESSA) Figure 11-3 Program Apparent.verties of Solutions ee en er 507 Procedure CalcApparentMolalvolumes; var I: integer; Begin Writeln;Writeln('molality density Apparent Molal Volume’); Writeln(' m da For I:= 1 to N do : : writeln(m(I}:6:3, @[I]:10:3,Phi(m[I],d[I]) 21623); NaCl") ; End; (JASE UE GSO ISIE ISI IID IOI SIS III II SII III I) Begin (* MAIN PROGRAM *) GetData; CalcApparentMolalVolumes; End. Figure 11-3 (continued) are pulled in. After 10 to 15 minutes for temperature equilibration, adjust the amount of liquid so that it is full exactly to the mark at 25°C. Do this by holding a piece of filter paper against the end of one arm of the pycnometer and tilting the pycnometer so that a small amount of water is drawn into the filter paper. Keep the main body of the pycnometer immersed in the thermostat bath while adjusting the water level. It is important to eliminate errors due to variation in the weight of the invisible layer of moisture on the surface of the pycnometer and its supporting hook. Always treat the pycnometer surface in exactly the same manner before weighing. After removing it from the thermostat, wash the outside of the pycnometer with distilled. water, dry it carefully with a clean, dry cloth, and let it hang in the balance room for 10 minutes before weighing. To check your experimental technique, determine the mass of water contained in your pycnometer with two independent mea- surements. They should agree to within +0.01%. If they do not, see your instructor before proceeding. Measure the density of the sodium chloride solutions, taking the same care used in calibrating the pycnometer. Results and Calculations The weight of the liquid in the pycnometer should be corrected for buoy- ancy (Lewis and Woolf, 1971). The corrected weight is given by dae ts dig us where Wiig is the corrected weight of the liquid, Wuns is the total mass of the balance weights, d,i, equals 0.0012 g/ ml, and dy. is the density of Wiig = Wons + Weal (11-26)508 Experimen Program Partial; uses crt; Const M1 = 18.01; (* molecular weight of solvent, water *) M2 58.443; (* formular weight of solute, NaCl *) dal 0.99707; (* density of water at 25.0 deg C *) nl = 55.51; (* moles of water in 1000g *) ArrayLength = 20;(* maximum allowed data pairs *) Type Ary = Array[1..ArrayLength] of Real; var Slope: Real; (* slope of phi vs. sq.rt. of molality *) m,phi: Ary; (* arrays of input molalities and *) (* apparent molal volumes *) N: Integer; (* requested number of input pairs *) GORE IIS III III II TOTTI ITS ITT TTI IIT III II III IIA) Function Vbarl(m,slope: real): real; Const n =1.57 var M32: real; (* molality to the 3/2 power *) Begin . M32:= exp(n*ln(m)); (* molality to the 3/2 power *) Vbarl:= ((M1/d1) - (m32*slope)/(2#n1)); (* equation (25) *) End; (* Vbarl *) (GEIS ISI IO ISIS TOSI ISTO OSI ITI IAD ISI III ITI TT IIT IIT II IIIS ISA) Function Vbar2(m,slope,phi: real): real; Begin Vbar2:= Phi + SQRT(m)*slope/2; End; (* Vbar2 *) (FEES IG IOS TOE ISO IO IIS IO IIE I IO a III TOTTI IS IIIT IIIT IST IIIA) Procedure GetData; Var I, X,Y: Integer; Begin CLRSCR; Write('How many molality, apparent molal vol pairs do you wish to input? '); Readln(n); Write('What is the slope of your plot of '); Writeln('apparent molal volume vs. SQRT(molality)?'); Writeln;Readln(slope) ;Writeln; Writeln('Please enter your ',N:1,' data pairs.'); For I:= 1 to N do . Begin Writeln; Write('molality # ',I:1,': ')? X:= Wherex;Y:= WhereY; Read(m{I})7 GoOTOXY (X+10,Y) 7 write('! Phi # ',I:1,': ')3 Readln(Phi(I}); End; (* For *) End; (* GetData *) Figure 11-4 Program Partial.perties of Solutions var I: Integer; Begin CLRSCR; Writeln; Writeln(' Writeln; Begin Begin (*MAIN GetData; End. GOH A IOS OSE ISSO I IOS IE ISSDO FEIT TOOT TOI I III IIE) Procedure CalcApparentMolalVolumes; Writeln(' molality apparent molal Partial molal Partial molal'); For I:= 1 to N do Write(m[I]:8:3,Phi[I]:17:3,Vbarl(m[I],slope) :15:3); Writeln(Vbar2(m[I],slope,phi[{I]) 15:3) End; (* For *) End; | (* CalcPartialMolalVolumes *) (GEIS I ORIG TSO TOG I TORII TOOT ICI ISI III IIS IIIT IIIT IIA III IIH) CalcApparentMolalVolumes; 509 volume volume water volume NaCl'); PROGRAM *) Figure 11-4 (continued) the balance weights. The density of brass is 8.4 g/ml and the density of stainless steel is 7.8 g/ml. The weights of single-pan balances are usu- ally stainless steel, while the weights used with chain balances are nor- mally brass. With Equation 11-20 calculate the apparent molal volumes of the solute for each solution, and plot @V against Vm. Determine the slope of the line d¢ vjaVm by least squares, and note the standard deviation. For each solution, calculate V, and V, with Equations 11-25 and 11~22, respectively. - To ease the tedium of the calculations, two computer programs are given in Figures 11-3 and 11-4. They could easily be linked together with a least-squares program into a single program that would calculate all the required quantities by simply furnishing the molalities and den- sities. It is preferable, however, to plot the apparent molal volumes and critically examine the data before proceeding. If you use a computer to carry out the calculations, furnish a sample calculation for one solution verifying the output for the apparent molal volume, and the partial molal volume for the solute and solvent for the given molality. REFERENCES 1. Bauer, N., and S. Z. Levin, in A. Weissberger and B. W. Rossiter, eds., Tech- niques of Chemistry, vol. 1, Physical Methods of Chemistry, pt. IV, chap. I, Wiley-Interscience, New York, 1972. 2. Klotz, I. M., Chemical Thermodynamics, chap. 13, Prentice-Hall, Englewood .,) Cliffs, New Jersey, 1950.