CHEM 254 PHYSICAL CHEMISTRY LABORATORY

Solubility and Enthalpy of Fusion of Ammonium Oxalate in Water

Oya Ilke Senturk 1792324

Section-03: Wednesday Afternoon Date of the experiment: 17.04.13 Group number: 11 Group Members: Pakizan Tasman Ozge Arman Name of the assistant: Fulya Kanik

CALCULATIONS: I. Calculation of solubility of ammonium oxalate

5C2O42-(aq)+2MnO4-(aq)+16H+(aq)-->10CO2(g) + 8H2O(l) + 2Mn+2(aq) M(KMnO4)xV(KMnO4)=n(KMnO4) na1=5/2x n(KMnO4) dsolution=1 g/mL; 5mL of solution is 5 g mass (water)= 5g-mass(ammonium oxalate) solubility= [mass(ammonium oxalate)/mass (water)]x100 T1=0.3 C nKMnO4=4.9x10-3Lx0.02M =9.8x10-5mol nA1=5/2nKMnO4=2.45x10-4mol nA2=4x 2.45x10-4mol = 9.8x10-4mol mass((NH4)2C2O4)=124.1g/mol x nA2 =124.1g/mol x9.8x10-4 mol=0.121618g d=1 g/ml 5 ml soln=5 g soln m(solvent )= 5g 0.121618g = 4.878 g solubility = m((NH4)2C2O4)/ m(solvent )x 100=0.121618g/4.878 x 100 =2.49% T2=21.3 C nKMnO4=10.2 x10-30.02=2.04 x10-4 mol na1=(5/2)x2.04 x10-4=5.1x10-4 mol na2 = 4 na1=45.1x10-4=2.04x10-3mol mass((NH4)2C2O4) = na2(Mwt)= 2.04x10-3x124.10=0.253 g msolvent = 5g -0.253=4.74 g S= (0.253/4.74)x100= 5.33% T3=85.5 C nKMnO4=19.3x10-30.02=3.86x10-4 mol na1=(5/2)x3.86x10-4 mol=9.65x10-4 mol na2= na1(27.5/5)= 9.65x10-4(27.5/5)=5.307x10-3 mol

mass((NH4)2C2O4) = na2(Mwt)= 5.307x10-3124.10=0.659 g msolvent = 5g -0.659= 4.3413 g S=( 0.659/4.3413)= 15.18 % II. Mole fraction of (NH4)2C2O4

At T1=0.3 C xB[(NH4)2C2O4]= 9.8x10-4/(9.8x10-4+0.271)= 3.603x10-3 lnxB=-5.63 At T2=21.8C xB[(NH4)2C2O4]= 2.04x10-3/ (2.04x10-3+0.2637)= 7.68x10-3 lnxB=-4.87 At T3=85.5C xB[(NH4)2C2O4]= 5.30x10-3/(5.30x10-3+0.2412)= 0.0215 lnxB=-3.84 III. Calculation of fusH of [(NH4)2C2O4]

lnxB vs. 1/T

0 0 -1 -2 lnxB -3 -4 -5 -6 1/T(K-1) y = 0.895x - 6.57 0.5 1 1.5 2 2.5 3 3.5

y = 0,895x - 6,57 slope= fusH/R 0.8958.3145= 7.44 kJ.mol-1= fusH

QUESTIONS: 1. A saturated solution is a solution in which the maximum amount of solute has been dissolved. In other words, it is the maximum concentration of a solution. Any solute added to the solvent after the solution reaches its saturation point will not dissolve and will remain as a precipitate. 2. 16 mol hydrogen ion is used for titration reaction of every five mole of oxalate with potassium permanganate. In other words, lots of hydrogen ion is needed for this titration and it can be obtained from a strong acid. H2SO4 provides the ions needed and it is unreactive towards the other chemicals used in the titration. 3. Since the solution whose solubility decreases with decreasing temperature is saturated at 85.5C, it begins to crystallize at lower temperatures. When using a pipette that is colder than the solution, crystals form and stop liquid flow into the pipette. This is not the case for Landolt pipette. It quickly draws the liquid up and prevents the procedure to be affected by those crystals by its filter. This filter stores the liquid. Moreover, it is not possible to measure volume of crystals by using regular pipette while it is with Landolt pipette. DISCUSSION In this experiment, solubility and enthalpy of fusion of ammonium oxalate in water was determined. Saturated solutions of ammonium oxalate were prepared at various temperatures and mass of ammonium oxalate dissolved is determined by titrating it against a known concentration of potassium permanganate solution. Solubility was determined by using these mass values as 2.49% at 0.3C, 5.33% at 21.8C and 15.18% at 85.5 C. Solubility increases with increasing temperature. Thus, it can be said that this process is an endothermic process, i.e. it is an endothermic solution. Using mole fraction of solvent molecule at equilibrium at that temperature, lnxB vs. 1/T graph is plotted and fusH was calculated by using slope of this graph. Experimental value of fusH is 7.44 kJ.mol-1. It has % error. This error might be caused from several reasons. Firstly, mass of solvent dissolved at equilibrium is needed for this experiment. If the system is not allowed to reach the equilibrium, there will be negative error in solubility values. Secondly, some substance may be lost during solution collection via pipettes. This also causes negative error. Moreover, this titration method is not very precise since it depends on human eye. Briefly, it was not possible to obtain precise values by using these methods which are vulnerable to be affected by human errors. REFERENCES http://pubs.acs.org/doi/abs/10.1021/ja01314a049