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Introduction
Solubility in water
> Water: dipolarity *shes very friendly kay ionic cpds] ion-dipole interaction > Lattice E, Hydration E, Heat of solution
Objectives
Determine enthalpy of solutes using calorimetric method Determine differential heats of solution of solute and solvent
Experimental
Procedure
calorimeter. determine calorimeter constant. tap and ice water (exp 6)
syringe. 20 mL distilled water to calorimeter. 15 mins. measure temp. weigh 1.0 0.01 g of salt in a watch glass. add to calorimeter with water. Measure temp every 5 sec. 10 readings.
Procedure
repeat above procedure for 1.50, 2.0, 2.50, and 3.0 g of salt.
repeat. 18, 16, 14, 12 mL water, 1.0 g of salt. do everything for each salt: CaCl2, NaCl, KCl, KBr, KI
Experimental Results
Results
WKI (g) 1.01 1.50 2.00 VH2O (mL) 20 20 20 Ti (oC) 30 29.3 28 Teq (oC) 28.2 27.2 25.5 Qsoln (J) 150.10 175.36 208.83 Hsoln (kJ/ mol) 24.67 19.41 17.33
nKI
0.00608 0.00904 0.01205
nwater
1.1063 1.1063 1.1063
2.50
3.00
20
20
0.01506
0.01807
1.1063
1.1063
27.8
27
24.2
23.7
300.75
275.75
19.97
15.26
Results
WKI (g) 1.00 1.00 VH2O (mL) 20 18 nKI 0.00624 0.00624 nwater 1.1063 0.99565 Ti (oC) 30 27.1 Teq (oC) Qsoln (J) Hsoln (kJ/ mol)
1.00
1.00 1.00
16
14 12
0.00624
0.00624 0.00624
0.88502
0.77439 0.66376
27
26.5 26
Results
Partial Molar Heat of Solution of KI
30
25
0 0 0.002 0.004 0.006 0.008 0.01 0.012 0.014 0.016 0.018 0.02
moles of KI
Results
Partial Molar Heat of Solution of Water
0.18 0.16
Heat of Solution 0.08 0.06 0.04 0.02 0 0 0.2 0.4 Linear (Heat of Solution)
moles of water
0.6
0.8
1.2
Results
Salt W of salt (g) CaCl2 1.01 NaCl 1.0 KCl 1.0 KBr 1.0 KI 1.01
V H2O (mL)
Moles of salt Moles H20 Ti (oC) Teq(oC) Qsoln (J) Hsolution (kJ/mol)
22.15
9.55x10-3 1.229 27 28.5 -341.987 -35.8 2197[7] 2567.30 J
20
2.566x10-2 1.105 29 28.5 45.145 1.75936 788.0 kJ[6] 849.72 J
20
1.34x10-2 1.106 30.7 28.1 277.483 20.71 708.8 kJ[6] 753.84 J
20
8.34x10-2 1.11 32 30 1032 122.43 679.5 kJ[6] 719.986 J
20
6.08x10-3 1.11 30 28.2 150.628 24.774 893.76 kJ[6] 671.7229 J
Hlattice (Born-Haber)
Hlattice (Kapustinskii) Hhydration (kJ/mol)
-33.2
0.85148
0.77455
0.842416
0.696496
Discussion
Discussion
IONIC COMPOUNDS > have very large attractive forces between oppositely charged ions in crystal lattice > high MP and BP > difficult to separate > e.g. ionic salts: NaCl, KCl, KI
Discussion
SOLUBILITY > a characteristic property of most ionic compounds SOLUTION > ions in solution are nearly independent of one another
Discussion
Then, how can ionic compounds dissolve at room temperature?
This is due to interactions between the ions and the molecules of water. (or other polar solvents)
> ion-dipole force!
Discussion
WATER is dipolar
> Negative (O) ends of water are strongly attracted to (+) ions > Positive (H) ends of water are strongly attracted to (-) ions As a result, water molecules cluster around an ion within their vicinity HYDRATION
Discussion
From: http://chemed.chem.wisc.edu/chempaths/GenChem-Textbook/Hydration-of-Ions-943.html
Discussion
Process of Solution (E Solution) (i) > 1st: crystalline salt gaseous ions (LATTICE E) (ii) > 2nd: water molecules surround the ions (HYDRATION E) (iii)
Discussion
G = H - TS SPONTANEOUS > (-) G (Change in Gibbs free E) > (-) H (Enthalpy Change) exothermic > (+) S (Entropy Change) > high T (Temperature)
Discussion
ENTROPY S > S - disorderliness - number of possible arrangements > solid < liquid < gas > usually drives endothermic reaction to become spontaneous
Discussion
Entropy > increases when crystalline salt is converted to gaseous state ions more disordered > decreases during hydration water molecules arrangement become limited > to achieve G , entropy INCREASE in forming gaseous ions MUST outweigh entropy DECREASE due to hydration
Sr2+
Al3+
-46.0
-
+10.9
-209
-52.0
-332
-71.6
-360
-90.4
-378
-3.4
-
+17.7
-
-8.7
-318
Born-Haber Cycle
The Born-Haber thermochemical cycle is named after the two German physical chemists, Max Born and Fritz Haber, who first used it in 1919. formation of an ionic compound from the reaction of an alkali metal (Li, Na, K, Rb, Cs) with a gaseous halogen (F2, Cl2) used to calculate Lattice E (in the expt)
Born-Haber Cycle
Born-Haber Cycle
Hsublimation - heat absorbed when 1 mol of atom is vaporized Hionization (IE) - remove an electron from an isolated atom or molecule Hdissociation (BDE) - energy involved in bond cleavage Helectron affinity (EA) - energy released when an electron is added to a neutral atom or molecule to form a negative ion Hlattice - energy absorbed when 1 mol crystal is formed Hformation - energy absorbed when 1 mol of atoms is formed
Kapustinskii equation
Anatolii Fedorovich Kapustinskii (1906-1960)
> Russian. Physical chemist. InorgChem.
to calculate:
> Lattice Energy [difficult to determine experimentally] > ionic radii [given the lattice energy]
generalized form of the Born-Lande equation [averaged Madelung constant] , does not depend on structure
Calculations
Formulas Used
1. moles: n = (mass)(1/MW) = (V)()(1/MW) 2. Qcal + Qtap + Qcal = 0 3. Qcal = CcalT 4. Qwater = (VH2O)(H2O)(spHeat) (4.184 J/goC)(T) 5. Hsoln = Qsoln + Qwater 6. Qcal + Qsoln + Qwater = 0 7. Hsoln = Qsoln /n 8. Kapustinskii (next slide) 9. Hsublimation + Hionization + HI-I bond enthalpy + Helectron affinity Hformation - Hlattice = 0 10. Hhydration = Hsoln - Hlattice
Formulas Used
Kapustinskii Equation K= 1.20254 Jm/mol d = 3.45E-11 m V = number of ions in empirical formula z = charge of cation/anion r = ionic radius
Calorimeter Constant
From equations 2 and 3, we get, Ccal = - [(Qcold + Qtap )]/(Ti,tap Teq)
Sample Calculations
Partial Molar Hsoln of KI (20mL, 1.50 g) nKI = 1.50 g(1mol KI/166.0028 g) = 0.009036 mol nH2O= [20mL(0.996175g/mL)] = 1.10686 mol (18g/mol) Qcal =(0.16961936 J/oC)(27.229.3oC) = - 0.3562 J Qwater=(20mL)(0.99586g/mL)(4.184J/goC)(27.229.3oC)
= - 174.99961 J Qsoln = -[(-0.3562) + (-174.99961)] = 175.36 J Hsoln = 175.36 J/0.009036 mols = 19.41 kJ/mol
Sample Calculations
Partial Molar Hsoln of water(20mL, 1.0 g) nKI = 1.0 g(1mol KI/166.0028 g) = 0.006024mol nH2O= [20mL(0.996175g/mL)] = 1.10686 mol (18g/mol) Qcal =(0.16961936 J/oC)(28.2 30oC) = - 0.3053 J Qwater=(20mL)(0.995646g/mL)(4.184J/goC)(28.230oC) = - 149.96818 J Qsoln = -[(-0.3562) + (-174.99961)] = 150.27 J Hsoln = 150.27 J/1.10686 mols = 0.136 kJ/mol
Sample Calculations
The Born-Haber cycle for Hlattice K(s) K(g) Hsublimation = +89.24 kJ K(g) K+ (g)+eHionization = +418.8 kJ 0.5 [I2(g) 2I(g)] HI-I bond enthal = +151(0.5) kJ 0.5[2I(g)+2e- 2I-(g)] He affinity = -295.16(0.5) kJ K+(g)+ I-(g) KI(s) -Hlattice
KI(s) K(s) +
1 I2(g) 2
Sample Calculations
Hlattice = Hsublimation + Hionization + HI-I bond enthalpy +Helectron affinity Hformation, KI(s) = [89.24 + 418.8 + (151)(0.5) + (-295.16)(0.5)] (-457.8) kJ = 893.76 kJ
-Hlattice = -893.76 kJ
Sample Calculations
The Kapustinskii Equation for Hlattice Hlattice = 1.2025E4 Jm/mol 2 +1 1 * + 15210 9 + 20610 9 3.4510 11 (1 ) 15210 9 + 20610 9 = -671.7224 J Hhydration of KI Hhydration = Hsolution - Hlattice = 24.774 (-671.7229) J = 696.496 J
Conclusion Recommendations
> Know your periodic table trends: ionic radii, ionization energy, electron affinity etc. > Careful on signs of delta Hs etc.
Q and A Portion
Q: How many physical chemists does it take to change a light bulb?
A:Only one, but he'll change it three times, plot a straight line through the data, and then extrapolate to zero concentration.
Cation radius
400
300 200 100 0 0 50
100
200
250
References
1. http://www.rod.beavon.clara.net/solubility.htm 2. http://chemistry.tutorvista.com/inorganicchemistry/reaction-pathways-born-haber-cycle.html 3. http://www.slideshare.net/janetra/6-the-born-habercycle 4. http://chemed.chem.wisc.edu/chempaths/GenChemTextbook/Hydration-of-Ions-943.html 5. http://www.docbrown.info/page07/delta2H.htm 6. http://www.science.uwaterloo.ca/~cchieh/cact/applyche m/lattice.html 7. http://chemistry.bd.psu.edu/jircitano/BH.html 8. http://chemistry.about.com/b/2007/03/24/periodictable-trends.htm