Title: solvolysis of the salt of a weak acid and a weak base.

Objective: to determine the extent of solvolysis of ammonium borate in water by calorimetry. Results: 25ml of 1.75M NaOH with 100ml of 0.5M HCl Time, t (sec) 60 120 180 240 309 313 320 348 408 468 528 588 Temperature, T (C) 25.0 25.0 25.0 25.0 27.0 28.0 28.5 29.0 29.0 29.0 29.0 29.0

25ml of 1.75M NaOH with 100ml of 0.5M H3BO3 Time, t (sec) 0 60 120 180 240 306 310 313 336 396 456 516 576 Temperature, T (C) 25.0 25.0 25.0 25.0 25.0 26.0 26.5 27.0 27.5 27.5 27.5 27.5 27.5

25ml of 1.75M NH4OH with 100ml of 0.5M HCl Time, t (sec) 0 60 120 180 240 302 306 308 329 389 449 509 569 Temperature, T (C) 25.0 25.0 25.0 25.0 25.0 25.0 26.0 26.5 27.0 27.0 27.0 27.0 27.0

25ml of 1.75M NH4OH with 100ml of 0.5M H3BO3 Time, t (sec) 0 60 120 180 240 307 313 330 390 450 510 570 830 Temperature, T (C) 25.0 25.0 25.0 25.0 25.0 25.5 26.0 26.5 26.5 26.5 26.5 26.5 26.5

Calculation: Based on the graphs, The values of T in mixtures of; a) 25ml of 1.75M NaOH with 100ml of 0.5M HCl = 4.0C b) 25ml of 1.75M NaOH with 100ml of 0.5M H3BO3 = 2.5C c) 25ml of 1.75M NH4OH with 100ml of 0.5M HCl = 2.0C d) 25ml of 1.75M NH4OH with 100ml of 0.5M H3BO3 = 1.5 C The mole of NaOH used is Mole = MV / 1000 = (1.75M)(25cm3) / 1000 = 0.04375 mol The mole of HCl used is Mole = MV / 1000 = (0.50M)(100cm3) / 1000 = 0.05 mol

Limiting mole is NaOH, hence the enthalpy of neutralisation is as such; -13.36 k cal mol-1 x 0.04375 = -0.5845 k cal Heat released = - q Therefore, -q1 = msolutionCsolution T + Ccalorimeter T - (-0.5845 x 103 cal) = (125g) (1 cal C-1g-1) (4C) + Ccalorimeter (4C) Ccalorimeter = (584.5cal -500cal) / (4C) = 21.125 cal C-1 -q4 = (125g) (1 cal C-1g-1) (2.5C) + (21.125) (2.5C) = 365.3 cal -q5 = (125g) (1 cal C-1g-1)(2.0C) + (21.125)(2.0C) = 292.3 cal q6 = q4 +q5 q1 = (-365.3cal -292.3cal) -(-584.5cal) = -73.1 cal Theoretical q is calculated as such; -q= (125g) (1 cal C-1g-1)(1.5C) + (21.125)(1.5C) = 219.2 cal Fraction of the salt ammonium borate that reacts with water when dissolved in water is calculated as such where is the value when the reactants are mixed in exactly equimolar amount.

 = = 219.2 cal / 73.1 cal =3 The value of is the fraction of the salt ammonium borate that undergoes solvolysis = 1 - =13 =-2 Hence the value of equilibrium constant can be identified using the relationship between Ksolvolysis and , where; Ksolvolysis =

= = 4/9

Given that KW is 1 x 10-14 and Kb is 1.75 x 10-5 for ammonia, the value of Ka of boric acid can be found as shown below; Ksolvolysis = Ka = (1 x 10-14 ) / ( 4/9 x 1.75 x 10-5) = 1.286 x 10-9

The published value of Ka of boric acid is 7.3 x 10-10 With this, the percentage of error is x 100% = 76.2% Discussion: Based on the results and calculations, the heat released decreases as the strength of acidity and basicity reduces. The heat change of each reaction is tabulated in the table below; Reactions 25ml of 1.75M NaOH with 100ml of 0.5M HCl 25ml of 1.75M NaOH with 100ml of 0.5M H3BO3 25ml of 1.75M NH4OH with 100ml of 0.5M HCl 25ml of 1.75M NH4OH with 100ml of 0.5M H3BO3 Heat Released (Exothermic) (cal) 584.5 365.3 292.3 219.2

Heat evolved during reactions decreases because the reactions are incomplete as the strength of acid or base decreases. The calculated q6 is higher than the observed value of q. The reason is that the reaction does not go to completion so the heat that is supposed to evolve and the observed heat change of reactant is different. According to the published value of Ka of boric acid, the percentage error is high, approximately 7.3 x 10-10 . This is owes to external factors such as the type of material the calorimeter is made up of as well as the efficiency of the calorimeter. Internal factors

such as the temperature change was not clearly recorded together with the mishandling of apparatus would also apply to the inaccuracy in the reading. The results were taken from a group of students in Lab Practical 3 as the results in my group were inaccurate and there were several discrepancies when the values obtained were substituted into the calculations above. Conclusion: 1) 2) 3) The value of calculated Ka of boric acid is 1.286 x 10-9. The heat capacity of calorimeter is 21.125 cal C-1. The equilibrium constant for the solvolysis constant is 0.44

Reference: http://chemed.chem.purdue.edu/genchem/topicreview/bp/ch17/ph.php#ka

Graph: 25ml of 1.75M NaOH with 100ml of 0.5M HCl

temperature (C) against time,t

29.5 29.0 28.5 28.0 27.5 27.0 26.5 26.0 25.5 25.0 24.5 0 100 200 300 400 Time, t (seconds) 500 600 700

25ml of 1.75M NaOH with 100ml of 0.5M H3BO3

temperature (C)

temperature (C) against time,t

28.0

temperature (C)

27.5 27.0 26.5 26.0 25.5 25.0 24.5 0 100 200 300 400 500 600 700 Time, t (seconds)

25ml of 1.75M NH4OH with 100ml of 0.5M HCl

temperature (C) against time,t

27.5

temperature (C)

27.0 26.5 26.0 25.5 25.0 24.5 0 100 200 300 Time, t (seconds) 400 500 600

25ml of 1.75M NH4OH with 100ml of 0.5M H3BO3

temperature (C) against time,t

26.6 26.4 26.2

temperature (C)

26.0 25.8 25.6 25.4 25.2 25.0 24.8 0 100 200 300 400 500 600 700 800 900 Time, t (seconds)