Piysical Chemistry | Laboratory Experiment No. 2 MEASUREMENT OF DENSITY AND DETERMINATION OF PARTIAL MOLAR VOLUME OF ETHANOL-WATER SYSTEM OBJECTIVES «To be familiarized with the use of the pycnometer and the chain balance for measuring density and specific gravity, respectively + To determine the partial molar volume of ethanol-water system at different concentrations using density and specific gravity measurement BACKGROUND Volume is, to a good approximation, an additive property. Certainly, this approximation is used in preparing solutions whose concentrations may not require @ high degree of accuracy. However, the standard method of preparing solutions of concentrations of known accuracy is not the addition of a weighed amount of solid te a known volume of solvent, but the addition of solvent, while mixing, to a weighed amount of solid until the final volume reaches the desired value: To prove, 1.000 g {X} / 10.00 mL H20 and 1.000 9{X} / 10.00 mL solutions are not identical. When a specie becomes part of a mixture, it loses its identity; yet it still contributes to the properties of the mixture, since the total solution properties of the mixture depend on the amount of each specie present and its resultant interactions. The thermodynamic properties of a mixture are affected both by the like and by the un- like interactions, that is, how each of the species in the mixture interacts with all of the other species it encounters. Partial molar quantities are key elements in the thermodynamics of solutions. We have seen that the combined first- and second laws for an open system is written, dU = TdS - pdV + uidny +H 2dnz +. qa) where the initial definitions of the pare given by,Physeal Chemistry 1 Laboratory wv) ev, ° ‘4n equivalent and more easily understood definition of the Is yiven by, ee me ES _— se 1y;{s called the "chemical potential" and it can be described in words as the Gibbs free energy per mole of substance. Another name for this quantity is "partial molar Gibbs free energy." We have found out that, using the integrated form of equation 1 and the definition of the Gibbs free energy, the Gibbs free eneray could be written as, G= pam thang +. @) Equation 4 is an exact thermodynamic equation and contains no approximations. Notice in equation 3 that jis intensive, It Is given by the extensive G divided by the extensive n,, Also, the variables thet are being held constant are temperature and pressure along with the number of moles of the other components of the system. We can define an equation similar to Equation 3 for any extensive property. The partial molar Gibbs free energy is the most important of these because It provides a measure of the “driving force" for chemical processes. The next most important of these quantities is the partial molar volume, (Bean ° The bar over the symbol indicates partial molar quantities. The partial molar volume in equation 5 can be thought of in several ways. it is the incremental volume obtained by adding a small amount of component / to the mixture while holding the temperature, the pressure, and the number of moles of all the other components constant divided by the number of moles of component /. Another way to look at it is to say that it is the incremental volume obtained by adding one mole of component / fo an infinite sample of the mixture. The partial molar volume is not necessarily the ‘of one mole of the pure component. (The intermolecular \of one component and molecules of other components belt bia tlPhysical Chemistry I Laboratory y be different from the interaction of molecules of a component with other lecules of the same component.) 1 is regarded as a function of temperature, pressure and composition, V = V(T, P, Rayon), then (Bo F and p are constant, equation 6 reduces to ) dp + Vidny + Vadng +... (6) P tn dV = Vidny + V2dn2 +... (7) Ich can be integrated to give, VenVi +n2V2 + zav (8) _e volumes given in equations 7 and 8 are the partial molar volumes which are not cessarily equal to the molar volumes: ‘of the pure components. Thus, equation 8 ggests that volumes may not be additive. That is, if we were to mix one liter of re ethanol with one liter of pure water, the final volume of the mixture would not ely be two liters. This is because water molecules interact with ethanol molecules ‘erently than they interact with other water molecules. easurement of partial molar volumes tere are several ways by which partial molar volumes can be measured. One way-!s. begin with one mole of a compound (call it component i), then add a small nount of component 2 and measure the volume, then add a little more of imponent 2 and measure the volume again. Keep doing this until the desired mmcentration range has been covered. Then fit the volume data to @ polynomial odel as follows: ny = 4,ng)= VP +anz +bn}/? send +... (9) ye constants, a, b, c, etc are obtained from the curve fitting and the first term is te molar volume of pure component 1. Then the partial molar volume of component can be obtained by direct differentiation,Physical Chemistry | Laboratory 3 =O+a+5bn3!? +2cng + i: (10) The partial molar volume of component 1 can be obtained from, Veni +mV2 = Vi +ngv2 (ay or Viz Vv-n2V2 (12) The last step is so because, in this case, n, is set to 1. . EXPERIMENTAL METHOD Equipment and Glassware 25 mL pycnometer; ensismefév “nalytical balance, 250-mL beakers, 25-mL graduated cylinder, — Reagents ethanol, distilled water Experimental Procedure A. Calibration of Pycnometer and Density Measurement Using Pycnometer 1. Prepare different concentrations (10% by volume increments) of ethanol- . water solutions. . 2. . Weigh a clean, dry pycnometer and label it as “empty”. 3. Fill the pycnometer with the sample to the brim and wipe dry the outside. 4. Re-weigh the pycnometer and label it as “pycnometer with sample”. 5. Remove the sample and dry the pycnometer in the oven. * 6. Repeat procedures 3 to 5 for the other remaining samples. 7. Determine the total volume of the pycnometer. Calculations The initial calculations should include: 1, mass of the solution inside the pycnometer 2. volume of the solution based on the volume of the pycnometer 16Pisco! Chemistry I Laboratory 3. density of the solution inside the pycnometer 4, mole fraction of ethanol in the solution 5. average molar mass of the solution 6. molar volume of the solution Repeat the calculation for the other samples. Specific Gravity Measurement using —Jensiomed’ 1. Prepare different concentrations (10% by volume increments) of ethanol water solutions. 2, Measure the specific gravity of the solution using the chain balance, Calculations The initial calculations should include: 1. specific gravity of the solution 2. density of the solution 3." mole fraction of ethanol in the solution 4, average molar mass of the solution 5. molar volume of the solution Repeat the calculation for the other samples. Evaluation of partial molar volume of ethanol-water system from the data in (A)i eae pu@yewoUdAd Je SUINION _uso/6 iL ye ueyem Jo Ay1sued 20 hb dajem yo eunjered wed Sranae qusjem + syawouddd Jo 24619 6 suayewwourkd Aadwe Jo 241M apyououdid 243 so UORRAAED "V _ ne an jn sss0qUieW rpauosied 22a —— on dnosp TasHs Viva WALSAS YALVM-TONVHLS 40 AWNIOA UVIOW WLLYVd 40 NOLLWNIWYALIG ONY ALISNAG JO LNSWSYNSVAN | Z ‘ON quewyedxa seepage 1 estoy 1218S