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Experiment 8: Lattice Enthalpy, Enthalpy of Solution and Enthalpy of Hydration Alma L. Pabilane and Lycelle S. Espaol Chemistry 156.

1 FEJ Group 8 Mr. Yevgeny Aster Dulla I. Abstract

Solution formation of an ionic compound in water involves two processes: the first, where the ionic compound is converted to its gaseous ions, involves lattice enthalpy (Hlattice); the second, where water molecules cluster around free ions, involves enthalpy of hydration (Hhydration). Conforming to Hess Law, enthalpy of solution is given by: Hsoln = Hlattice + Hhydration. Using calorimetry, Hsoln of the ionic salts CaCl2, NaCl, KCl, KBr and KI dissolved in water are determined. The calculated Hsoln for 1 g of salt dissolved in 20 mL water are -35.8, 1.76, 20.71, 122.43 and 24.77 kJ/mol, respectively. Experimental Hsoln for NaCl, KCl and KI are considerably near the theoretical values: 3.88, 17.2 and 20.5 kJ/mol, respectively. While that of CaCl2s and KBrs experimental Hsoln are not near the theoretical value (-82.9 and 20.0 kJ/mol), they showed the expected sign of H soln (endothermicity or exothermicity). The deviation may be due to experimental errors: ineffectiveness of improvised calorimeter, human error etc. Partial molar heat of solution (PMHS) of a reactant (salt or water) is given by the slope of the curve when number of moles of that reactant is plotted against the Hsoln with respect to the number of moles of that reactant. The PMHS of the 5 salts (KI, KCl, KBr, CaCl2, NaCl) are -612.3, -112.7, -1540.88, -382.10, and -90.82 kJ/mol, respectively while the PMHS of water determined for each salt are -0.054, -112.72, -321.93, -355.44, and -5.120 kJ/mol, respectively. The partial molar heat of solution signifies the amount of energy needed to break the solutesolute or solvent-solvent interactions for solution formation to proceed. Hlattice is estimated using Kapustinskii equation and Born-Haber Cycle. Kapustinskii yielded more precise value for Hlattice. It was observed that Hlattice decreases with increasing atomic radius for both anion and cation. The Hhydration was calculated by subtracting the Hlattice from Hsoln.

II. Keywords: Born-Haber cycle, Calorimetry, Enthalpy of solution, Enthalpy of Hydration, Kapustinskii Equation,
Lattice enthalpy

III. Introduction Dissolving a solute to form a solution involves the solvation of the solute in a particular solvent at specified conditions and is affected by the strength of the solute-solute, solvent-solvent, and solute-solvent interactions. This process requires the release (exothermic) or absorption (endothermic) of energy in the form of heat, and consequently, the characteristic solubility of ionic substances in water can be described by the enthalpy changes in a solution, namely; the lattice enthalpy, enthalpy of hydration and enthalpy of solution. The enthalpy of hydration (Hhydration) is the enthalpy change for the production of an ionic solution from one mole of gaseous ions. Directly dependent on the charge and inversely dependent on the atomic radii of the ions, enthalpy of hydration values are negative and are indicative of ion-water interaction. When solvents other than water are used, this enthalpy change is called the enthalpy of solvation. The lattice enthalpy (HLE or HLattice) is the enthalpy change for the formation of one mole solid from gaseous ions and is also the energy needed to break the crystal lattice of an ionic solid. Like the enthalpy of hydration, it is directly dependent on the ionic charge but inversely dependent on ionic radius.

Two methods can be used to determine the lattice enthalpy: the Born-Haber cycle, which uses measurable thermochemical data, and the Kapustinskii equation, which gives an approximation of the lattice enthalpy given the ionic charges and radii. The Kapustinskii equation for lattice enthalpy is given by, Hlattice = where, k = 1.2025x10-4 Jm/mol d = 3.45x10-11 m v = number of ions in the empirical formula of the substance z(+/-) = ionic charge of the cation/anion r(+/-) = ionic radius of the cation/anion The enthalpy of solution (Hsoln) is the enthalpy change for the formation of one mole of solution from one mole of a solute dissolved and can be calculated from the difference between the enthalpy of hydration of the ions and the lattice enthalpy. Generally, a negative enthalpy value indicates that the solute is soluble in a given solvent while a large positive value indicates otherwise.

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In the experiment, the goal was to determine the enthalpy of solution of different solutes (CaCl2, NaCl, KCl, KI, and KBr) using the calorimetric method and to determine the differential heats of solution of solute and solvent. IV. Experimental The calorimeter constant of an improvised Styrofoam calorimeter was initially determined. Using a syringe, 20 mL of distilled water was transferred into the calorimeter and incubated for 15 mins. to allow equilibration of heat. The equilibrium temperature was of water in the calorimeter was recorded. In a watch glass, 1.0 0.01 g of calcium chloride (CaCl2) crystals was weighed. Immediately, the CaCl2 crystals were added into the calorimeter. The temperature was read and recorded every five seconds while swirling the mixture in the calorimeter continuously until 10 temperature readings were obtained. The procedure was repeated with varying mass of CaCl2 1.5, 2.0, 2.5 and 3.0 g with constant volume of water 20 mL; and varying volume of water 18.0, 16.0, 14.0, 12.0 mL with constant mass of CaCl2 1.0 g. The procedure was repeated for other ionic salts in place of CaCl2: sodium chloride (NaCl), potassium chloride (KCl), potassium bromide (KBr) and potassium iodide (KI). The heat of solution of each salt was calculated using the following equations:

Ccal = [(10mL)(0.9997g/mL)(20-10oC)(4.184J/goC) + (10mL)(0.9956g/mL)(20-30oC)(4.184J/goC)]/(20-30oC) =0.1696 J/oC A. Determination of Partial Molar Heats of Solution A.1 Partial molar heat of solution of KI Table 1. Constant water versus varying KI
WKI (g) VH2O (mL) nKI nH2O Ti (oC) Teq (oC) Qsoln (J) Hsoln (kJ/mol) 1.01 20 6.08 x10-3 1.11 30 28.2 150.63 24.774 1.5 20 9.04 x10-3 1.11 29.3 27.2 175.61 19.426 2.0 20 0.012 1.11 28 25.5 209.21 17.434 2.5 20 0.015 1.11 27.8 24.2 301.26 20.084 3.0 20 0.0181 1.11 27 23.7 276.15 15.257 -612.3

Partial molar Hsoln of KI (kJ/mol)

Computations nH2O = 20mL(0.998g/mL)(1mol/18.01g) = 1.11 mol H2O Trial 1: Qcal = CcalT = (0.1696J/oC)(28.2-30oC) = -0.305 J QH2O = mH20(4.184 J/goC)(T) = (20mL)(0.998g/mL)(4.184 J/goC)(28.2-30 oC) = -150.323 J Qsoln = -( Qcal + QH2O) = -(-0.305J -150.323J) = 150.628 J nKI = 1.01g KI(1mol/166.00277g) = 6.084x10-3 mol KI Hsolution = Qsoln/nsalt =[150.628J(1kJ/1000J)] 6.08x10-3mol = 24.774 kJ/mol Trial 2: Qcal = CcalT = (0.1696J/oC)(27.2-29.3oC) = -0.237 J QH2O = mH20(4.184 J/goC)(T) = (20mL)(0.998g/mL)(4.184 J/goC)(27.2-29.3oC) = -175.377 J Qsoln = -( Qcal + QH2O) = -(-0.237J 175.377J)

Hsoln = Qsoln + Qwater Qcal + Qsoln + Qwater = 0

To calculate partial molar heat of solution of the salt, the number of moles of the salt (from Part 1, where mass of salt is varying and volume of water is constant) is plotted against the calculated Hsoln. For partial molar heat of solution of water, the number of moles of water (from Part 2, where volume of water is varying and mass of salt constant) was plotted against the corresponding Hsoln. V. Results Computing for the Ccal of the calorimeter used:

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= 175.614 J nKI = 1.50g KI(1mol/166.00277g) = 9.04x10-3 mol KI Hsolution = Qsoln/nsalt =[175.614J(1kJ/1000J)] 9.04x10-3mol = 19.426 kJ/mol Trial 3: Qcal = CcalT = (0.1696J/oC)(25.5-28oC) = - 0.424 J QH2O = mH20(4.184 J/goC)(T) = (20mL)(0.998g/mL)(4.184 J/goC)(25.5-28oC) = -208.782 J Qsoln = -( Qcal + QH2O) = -(-0.424J 208.782J) = 209.206 J nKI = 2.0g KI(1mol/166.00277g) = 0.012 mol KI Hsolution = Qsoln/nsalt =[209.206J(1kJ/1000J)] 0.0120mol = 17.434 kJ/mol Trial 4: Qcal = CcalT = (0.1696J/oC)(24.2-27.8oC) = -0.611 J QH2O = mH20(4.184 J/goC)(T) = (20mL)(0.998g/mL)(4.184 J/goC)(24.2-27.8oC) = -300.646J Qsoln = -( Qcal + QH2O) = -(-0.611J-300.646J) = 301.257 J nKI = 2.50g KI(1mol/166.00277g) = 0.0150 mol KI Hsolution = Qsoln/nsalt =[301.257J(1kJ/1000J)] 0.0150mol = 20.084 kJ/mol Trial 5: Qcal = CcalT = (0.1696J/oC)(23.7-27oC) = -0.560 J QH2O = mH20(4.184 J/goC)(T) = (20mL)(0.998g/mL)(4.184 J/goC)(23.7-27oC) = -275.592 J Qsoln = -( Qcal + QH2O) = -(-0.560J-275.592J) = 276.152 J nKI = 3.00g KI(1mol/166.00277g) = 0.0181 mol KI Hsolution = Qsoln/nsalt =[276.152J(1kJ/1000J)]

0.0181mol = 15.257 kJ/mol Using linear regression, plot Hsolution vs nsolute. Hsolution = nKIHsolution,KI + nH2OHsolution,H2O y = mx + b y = (-612.3)x + 0.161 m = partial molar heat of solution of KI = -612.3 kJ/mol

Figure 1. Graph for the determination of Partial Molar Heat of Solution of KI with the equation of the best fit line (inset)

The same procedure was done for the remaining salts, and the values are shown in the following tables. Table 2. Constant water versus varying KCl
WKCl (g) 1.0 1.5 VH2O 20 20 (mL) nKCl 1.34x10-2 0.0201 nH2O 1.106 1.11 30.7 26.9 Ti (oC) 28.1 23.5 Teq (oC) Qsoln (J) 277.48 379.79 Hsoln 20.71 18.88 (kJ/mol) Partial molar heat of solution of KCl (kJ/mol) 2.0 20 0.0268 1.11 26 21.5 502.67 18.74 2.5 20 0.0335 1.11 26 20.9 569.69 16.99 3.0 20 0.0402 1.11 26.5 20.0 726.07 18.04 -112.72

Table 3. Constant water versus varying KBr


WKBr (g) VH2O (mL) nBr nH2O Ti (oC) Teq (oC) Qsoln (J)

1.01 20 8.43 x10-3 1.11 32 30 1032

1.5 20 0.0126 1.11

2.0 20 0.0168 1.11

2.5 20 0.021 1.11

3.0 20 0.0252 1.11

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Hsoln (kJ/mol)

122.43

102.39

107.51

98.29

92.15 Computations: -1540.88 nKI = 1.01g KI(1mol/166.00277g) = 6.08x10-3 mol KI Trial 1: Qcal = CcalT = (0.1696J/oC)(28.2-30oC) = -0.305 J QH2O = mH20(4.184 J/goC)(T) = (20mL)(0.998g/mL)(4.184 J/goC)(28.2-30 oC) = -150.323 J Qsoln = -( Qcal + QH2O) = -(-0.305J -150.323J) = 150.628 J Hsolution = Qsoln/nsalt =[150.628J(1kJ/1000J)] 1.11mol = 0.136 kJ/mol Trial 2: Qcal = CcalT = (0.1696J/oC)(26-27.1oC) = -0.187 J QH2O = mH20(4.184 J/goC)(T) = (18mL)(0.998g/mL)(4.184 J/goC)(26-27.1 oC) = -82.678 J Qsoln = -( Qcal + QH2O) = -(-0.187J -82.678J) = 82.865 J nH2O = 18mL(0.998g/mL)(1mol/18.01g) = 0.998 mol H2O Hsolution = Qsoln/nH2O = 82.865J(1kJ/1000J) 0.998mol = 0.0830 kJ/mol Trial 3: Qcal = CcalT = (0.1696J/oC)(25.9-27oC) = -0.187 J QH2O = mH20(4.184 J/goC)(T) = (16mL)(0.998g/mL)(4.184 J/goC)(25.9-27oC) = -73.491 J Qsoln = -( Qcal + QH2O) = -(-0.187J 73.491J) = 73.678 J nH2O = 16mL(0.998g/mL)(1mol/18.01g) = 0.887 mol H2O Hsolution = Qsoln/nH2O = 73.678J(1kJ/1000J) 0.887mol = 0.0831 kJ/mol Trial 4: Qcal = CcalT

Partial molar heat of solution of KBr(kJ/mol)

Table 4. Constant water versus varying CaCl2


WCaCl2 (g) VH2O (mL) nCaCl2 1.01 22.12 9.55 x10-3 1.229 27 28.5 203.06 21.26 1.5 21.42 0.014 2.0 20 0.018 2.5 20 0.023 1.11 24.5 27.5 379.57 16.50 3.0 20 0.027 1.11 24 27.5 442.83 16.40 -382.10

nH2O 1.19 1.11 Ti (oC) 26 25 Teq (oC) 28.5 27.5 Qsoln (J) 331.13 316.31 Hsoln 23.65 17.57 (kJ/mol) Partial molar heat of solution of CaCl2 (kJ/mol)

Table 5. Constant water versus varying NaCl


WNaCl (g) VH2O (mL) nNaCl

1.01 20

1.5 20 0.025 6 1.11 29 28.5 45.22 9 1.763

2.0 20 0.034 2 1.11 29 28.5 45.22 9 1.323

2.5 20 0.0427 1.11 29.5 27.5 180.91 6 4.233

3.0 20 0.0513 1.11 28.5 27 135.68 7 2.646 90.815 4

0.017 1 nH2O 1.11 Ti (oC) 30 Teq (oC) 30 Qsoln (J) 0


Hsoln (kJ/mol )

Partial molar heat of solution of NaCl (kJ/mol) A.2 Partial Molar Heat of Solution of Water

Table 6. Varying water versus constant KI


WKCl (g) VH2O (mL) nKCl 1.01 20 6.08x1 0-3 1.11 30 28.2 150.63 0.136 1.0 18 6.08x1 0-3 0.998 27.1 26 82.865 0.0830 1.0 16 6.08x1 0-3 0.887 27 25.9 73.678 0.0831 1.0 14 6.08x1 0-3 0.776 26.5 25 87.942 0.113 1.0 12 6.08x1 0-3 0.665 26 24 100.55 0.151

nH2O Ti (oC) Teq (oC) Qsoln (J) Hsoln (kJ/mol ) Partial molar heat of solution of H2O (kJ/mol)

-0.0537

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= (0.1696J/oC)(25-26.5oC) = -0.254 J QH2O = mH20(4.184 J/goC)(T) = (14mL)(0.998g/mL)(4.184 J/goC)(25-26.5oC) = -87.688 J Qsoln = -( Qcal + QH2O) = -(-0.254J 87.688J) = 87.942 J nH2O = 14mL(0.998g/mL)(1mol/18.01g) = 0.776 mol H2O Hsolution = Qsoln/nH2O = J(1kJ/1000J) 0.776mol = 0.113 kJ/mol Trial 5: Qcal = CcalT = (0.1696J/oC)(24-26oC) = -0.339 J QH2O = mH20(4.184 J/goC)(T) = (12mL)(0.998g/mL)(4.184 J/goC)(24-26oC) = -100.215 J Qsoln = -( Qcal + QH2O) = -(-0.339J 100.215J) = 100.554 J nH2O = 12mL(0.998g/mL)(1mol/18.01g) = 0.665 mol H2O Hsolution = Qsoln/nH2O = 100.554J(1kJ/1000J) 0.665mol = 0.151 kJ/mol Using linear regression, plot Hsolution vs nH2O. Hsolution = nH2OHsolution,H2O + nKIHsolution,KI y = mx + b y = (-0.054)x + 0.161 m = partial molar heat of solution of H2O = -0.0537 kJ/mol

Table 7. Varying water versus constant KCl


WKCl (g) VH2O (mL) nKCl 1.0 20 1.34 x10-2 1.0 1.0 1.0 1.0

18
1.34 x10-2

16
1.34 x10-2

14
1.34 x10-2

12
1.34 x10-2

nH2O 1.11 0.998 0.887 30.7 26.9 26 Ti (oC) 28.1 23.5 21.5 Teq (oC) Qsoln (J) 277.48 379.79 502.67 Hsoln 20.71 18.876 18.737 (kJ/mol) Partial molar heat of solution of H2O (kJ/mol)

0.776
26 20.9 569.69 16.988

0.665
26.5 20.0 726.07 18.043

-112.72

Table 8. Varying water versus constant KBr


WKBr (g) 1.0 1.0 1.0 VH2O 20 18 16 (mL) nBr 8.396 8.396 8.396 nH2O 1.11 0.998 0.887 Ti (oC) 30 29.5 30 Teq (oC) 28.5 27.5 27.5 Qsoln (J) 761.5 998 588 Hsoln 90.70 118.94 146.18 (kJ/mol) Partial molar heat of solution of H2O (kJ/mol) 1.0 14 8.396 0.776 29 26 1227.315 186.79 1.0 12 8.396 0.665 25 1568 235.8

-321.93

Table 9. Varying water versus constant CaCl2


WCaCl2 (g) VH2O (mL) nCaCl2 nH2O Ti (oC) Teq (oC) Qsoln (J) 1.01 22.12 9.55 1.229 27 28.5 203.06 1.0 18 9.10 0.998 23.5 25.5 236.34 1.0 16 9.37 0.887 22.5 24 164.73 1.0 14 9.73 0.776 23 24.5 152.20 0.19613 1.0 12 9.37 0.665 22.5 24.5 186.24 0.28006

Hsoln 21.26 0.23681 0.18572 (kJ/mol) Partial molar heat of solution of H2O (kJ/mol)

-355.44

Table 10. Varying water versus constant NaCl


WNaCl (g) VH2O (mL) nNaCl nH2O Ti (oC) Teq (oC) Qsoln (J)

1.01 20 0.0171 1.11 30 30 0

1.0 18 0.0171 0.998 28 27 82.090

1.0 16 0.0171 0.887 28.5 28 36.861

1.0 14 0.0171 0.776 28 27 65.354

1.0 12 0.0171 0.665 28 27 56.986

Figure 2. Graph for the determination of Partial Molar Heat of Solution of H2O with the equation of the best fit line (inset)

Same calculations were done for the remaining salts, and the values are shown in the following tables.

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Hsoln (kJ/mol)

4.802

2.156

3.823

3.334 Ca2+ Na+ K+ HLE=

Partial molar heat of solution of H2O (kJ/mol)

-5.120

(pm) 114 116 152

ClBrI-

(pm) 167 182 206

B. Determination of Lattice Enthalpy and Enthalpy


of Hydration Table 11. Values for the Computation of Lattice Enthalpy and Enthalpy of Hydration
Salt Wsalt (g) VH2O (mL) nsalt nH2O Ti (oC) Teq (oC) Qsoln (J) Hsoln (kJ/mol) Hlattice (BornHaber) Hlattice (Kapust inskii) (J) Hhyd (kJ/mol) CaCl2 1.01 22.15 9.55 x10-3 1.229 27 28.5 -342.0 -35.8 -2197
[7]

NaCl 1.0 20 2.566 x10-2 1.105 29 28.5 45.145 1.759 -788.0


[6]

KCl 1.0 20 1.34 x10-2 1.106 30.7 28.1 277.48 20.71 -708.8
[6]

KBr 1.0 20 8.34 x10-2 1.11 32 30 1032 122.43 -679.5


[6]

KI 1.01 20 6.08 x10-3 1.11 30 28.2 150.63 24.77 -893.76


[6]

= -671.7224 J For Hhydration of KI Hhydration = Hsolution - Hlattice = 24.774 (-671.7229) J = 696.496 J

-2567

-849.72

-753.84

-720

-671.72

-33.2

0.8515

0.7745

0.8424

0.6965
Figure 3. The plot of the cation radius and the lattice enthalpies of CaCl2 NaCl and KCl with the equation of the best fit line (inset).

Sample computations for part B: Salt used: KI The Born-Haber cycle 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 enthalpy = +151(0.5) kJ 0.5[2I(g)+2e- 2I-(g)]Helectron affinity = -295.16(0.5) kJ K+(g)+ I-(g) KI(s) -HLE KI(s) K(s) + I2(g) Hformation, KI(s) = -457.8 kJ

-HLE = -[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 The Kapustinskii Equation Table 12. Cations, Anions and Ionic radii Cation Radius Anion Radius

Figure 4. The plot of the anion radius and the lattice enthalpies of KCl, KBr and KI with the equation of the best fit line (inset).

VI. Discussion Ionic compounds have very strong attraction between oppositely charged ions in their crystal lattice. Their high melting point and boiling point are proof of this. Due to this strong ionic attraction, two oppositely

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charged ions attached to each other are very difficult to separate. However, when these compounds are placed in aqueous solutions, they easily dissolve. This is because water molecules are dipolar. Their partial positive ends (hydrogens) are attracted to the negatively charged ion and the partial negative ends (oxygens) are attracted to the positively charged ions. Solution formation generally involves two processes: the first one is where the ionic salt crystals are converted to gaseous ions and the second one is when water molecules cluster around these free ions (as described in the previous paragraph). The first process involves the lattice dissociation energy, sometimes called crystal energy, which is the amount of energy released when from crystal form, the ionic compound is converted to a gas of its ions. The reverse of this process is the crystal formation. The second process is called hydration and involves enthalpy of hydration. Using the principle of Hess Law, the overall heat of solution is given by: Hsoln = Hlattice + Hhydration. Experimental measurements of change in enthalpies are usually done using the calorimetric method of which there are two types: the constant pressure (coffee cup) and the constant volume method (bomb). Due to availability, the former is used in the experiment to measure the change in temperature and to determine the change in enthalpy of the solution. For a solution of two components (the solute and the solvent), the enthalpy can be expressed as a function of the moles of the solute and of the solvent. Hsolution = nsoluteHintegral,solute + nsolventHintegral,solvent The partial molar heat of solution of the solute is the energy required to break the solute-solute interactions. The higher the value the harder it is for a solute to dissolve because the solute needs to absorb that amount of energy for it to be solvated. Based on the positive value of the partial heat of solution of the solute (see tables 1 through 5), increasing the number of moles of solute increases the heat of solution. This indicates that more energy is required to separate ions on the lattice. The heat of solution, however, increases until a certain number of moles of water and afterwards it already decreases. The experimental results failed to show this since upon increasing the number of moles of KI, the heat of solution decreased. Meanwhile, the partial molar heat of solution of the solvent is the energy required to break solventsolvent interactions. A low value indicates that the solvent can easily solvate a certain solute because the solvent needs a small amount of energy for the solventsolvent interaction to be broken. It was noted that increasing the moles of water makes the solvation of KI easier. This occurs until up to the extent when all of the solute are dissolved. Generally, as the moles of water

decreases, the heat of solution also decreases, as shown by the experimental results (tables 6 through 10). In the experiment, all salts except CaCl2 yielded a positive value for the enthalpy of solution, indicating that these salts must acquire a certain amount of energy for it to be dissolved. The energy absorbed by the salts was in the form of heat, hence the temperature of the solution decreased. The reverse can be said for CaCl2, which yielded a negative value for the enthalpy of solution and a rise in temperature upon dissolution. This is characteristic of the hygroscopic nature of the salt, which needs to release a certain amount of energy in the form of heat upon solvation in water, hence the rise in temperature. (see tables 1 through 5 for the values) Exothermic reactions are the ones that usually proceed spontaneously. According to the fundamental equation: G = H TS, a more negative G signifies a more spontaneous process. Therefore, to have a (-) G, the term H should be negative, temperature (T) is desired to be higher, and there must be an increase in entropy, because the tendency of energy is to disperse as much as possible. For endothermic reactions, it is the entropy that makes the reaction spontaneous (still a negative G despite positive H). In the first process of solution formation (solid gas), entropy increases because entropy of gas is greater than that of solid. While in the second process (hydration), entropy decreases, because the arrangement of water molecules are limited, being that they are attracted to the free ions. But the dissolution of ionic salts, though endothermic, is still spontaneous because the increase in entropy in the formation of gaseous ions outweighs the decrease in entropy in formation of hydrated ions. The Born-Haber thermochemical cycle is named after the two German physical chemists, Max Born and Fritz Haber, who first used it in 1919. It is used to calculate for lattice enthalpy, since it is difficult to determine experimentally.

Figure 5. The Born-Haber Cycle: lattice formation of ionic salt from its initial components at standard state

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It describes 5 processes between the reaction of salt formation of alkali metal and gaseous halogen: sublimation of the alkali metal, dissociation of the gaseous halogen, ionization of gaseous metal to form a cation, accepting of electron of gaseous halogen to form anion, lattice crystal formation of the cations and anions. Overall, Hsublimation + Hionization + HI-I bond enthalpy + Helectron affinity Hformation - Hlattice = 0 Derived from the Born-Lande equation and used an averaged Madelung constant such that it can determine the lattice energy without considering the structure of the lattice, the Kaspustinskii equation was used as an alternative method of computing for the lattice energy. The equation shows the relationship of lattice energy to the ionic radius, charge and number of ions. Upon plotting the ionic radii against the lattice enthalpies of the solutes as seen in figures 3 and 4, it was noticed that the lattice enthalpy decreased as the ionic (both cationic and anionic) radii increased, and that the lattice enthalpy increases as the ionic charge increased. This followed the theoretical trend because an ion with large radius forms a long and weaker bond compared to an ion with a shorter radius. The weak ionic bond formed by large ions requires less energy for it to be broken. Meanwhile, a highly-charged ion forms a stronger bond than an ion with a lesser charge, hence more energy is needed to break the bond. VII. Conclusion and Recommendation Enthalpy of solution for an ionic compound in water is the sum of enthalpies of the reactions that occur in solution formation: lattice enthalpy and hydration enthalpy. Number, charge and ionic radii of ions involved in the lattice affect lattice enthalpy. Higer charges, more ions involved, greater the lattice enthalpy, while greater ionic radii of ions would result to smaller lattice enthalpy. The calorimetric method was relatively effective in determining the enthalpy changes of solution of different solutes, and the precursor values for the computation of the differential heats of solute and solvent. The Born-Haber cycle and the Kapustinskii equation were two methods used to calculate for the lattice enthalpy. Kapustinskii equation is more effective and accurate than Born-Haber, because it considers the ionic radii of the ions involved in the lattice. Born-Haber is more prone to error since it uses standard values, which are measured at standard temperature, while the actual experiment is not held at standard conditions. Based on the experimental data

gathered, the experimental results reflected the theoretical results well, albeit with deviations attributed to systematic and random error. It is therefore recommended to ensure the effectiveness of the set up as well as the efficiency of the proponents in measuring the temperature immediately after adding the salts. VIII. References: [1] Barbalace, K. (2011). Periodic Table of Elements Potassium - K. EnvironmentalChemistry.com. Retrieved September 30, 2011 from http://EnvironmentalChemistry.com/yogi/peri odic/K.html. [2] _____. (2011). Iodine element facts. Chemicool.com. Retrieved September 30, 2011 from http://www.chemicool.com/elements/iodine.ht ml. [3] _____. (2002). Experiment 8: Enthalpy of Solution, Lattice Enthalpy and Enthalpy of Hydration. Laboratory Manual in Physical Chemistry. Philippines: University of the Philippines Manila. [4] Clark, J. (2010) Lattice Enthalpy. Retrieved September 28, 2011 from http://www.chemguide.co.uk/physical/energe tics/lattice.html. [5] Snelling, R. (2008). Density of Water vs Temperature. Retrieved September 28, 2011 from http://www2.volstate.edu/CHEM/Denstiy_of_ Water.htm. [6] Huheey et. al., as cited by Sinex (2009). (1993). Inorganic Chemistry, 4th ed. USA: HarperCollins Publications. [7] _____. (n.d.). Module 4: Energetics. CCEA Advanced Subsidiary. Retrieved September 30, 2011 from http://20to9.com/PPN/GCE_Dedicated_Note s/mod4/Thermochemistry.pdf. [8] _____. (2002). Laboratory Manual in Physical Chemistry I. Philippines. [9] Clark, J. (2010). Enthalpies of Solution and Hydration. Chemguide. Retrieved September 27, 2011 from http://www.chemguide.co.uk/physical/energe tics/solution.html. [9] _____. (n.d.) Lattice Enthalpies. Retrieved September 27, 2011 from http://jcsu.jesus.cam.ac.uk/~rpc25/notes/che mistry/lattice_enthalpies/index.html. I hereby certify that I have given substantial contribution to this report.

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____________________________ Alma L. Pabilane ____________________________ Lycelle S. Espaol

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