(worksheet 1st

)
Drs. M. Hariyanto SMA Negeri 3 Malang (Public Senior High School) Jl. Sultan Agung Utara No 7 Phone (0341) 324 768 Malang 65111 (web site : http://www.har-chemist.co.nr )

Before we study about buffer solution, we should review the previous material, how to calculate the pH of acid, base, the mixture of acid and base, and Bronsted-Lowry theory of acid-base. Complete the following table!

1. pH of acid and base Solutions
H2SO4 0,005 M KOH 0,1 M HCOOH 0,1 M Ka =1 x 10-5 NH3 0,1 M Kb = 1 x 10-5

SA/WA/SB/WB
SA ………….. ………….. …………..

[H+] = a. Ma ………….. ………….. …………..

The formulae of [H+] or [OH-]

Calculation of pH
…………..………….. …………..………….. …………..………….. …………..…………..

SA = strong acid; WA = weak acid; SB = strong base; WB = weak base 2. pH of mixture No
1

The mixtures
10 mL of H2SO4 0.1 M is added to 90 mL of water. Calculate the pH of mixture! 800 mL of H2SO4 0.1 M is added to 200 mL of HCl 0.2M. Calculate the pH of mixture! 800 mL of Ca(OH)2 0.1 M is added to 200 mL of NaOH 0.2M. Calculate the pH of mixture! 800 mL of Ca(OH)2 0.1 M is added to 200 mL of HNO3 0.2M. Calculate the pH of mixture

React or not
Not react

The steps of solutions
Dilution ……………………………………… ……………………………………… ……………………………………… ……………………………………… ……………………………………… ……………………………………… ……………………………………… ……………………………………… ……………………………………… ……………………………………… ……………………………………… ……………………………………… ……………………………………… ……………………………………… ………………………………………

2

3

4

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3. The acid dissociation constant (Ka) and base dissociation constant (Kb)
a. The ionization of weak acid, HA 1) write the ionization of weak acid, HA in water 2) write the formulae of Ka

b. The ionization of weak base, LOH 1) write the ionization of weak base, LOH in water 2) write the formulae of Kb

4. The Bronsted-Lowry Theory of acid-base a. Determine the conjugate-base of acid and conjugate-acid of base Complete the blank column!
No 1 2 3 4 Acid H2O CH3COOH HCN NH4+ H+ H+ Conjugate-base + H+

No 1 2 3 4

Base H2O NH3 HCO3HPO42-

+ +

Conjugate-acid

b. Given that the reaction : CO32-(aq) + NH4+(aq) ↔ HCO3-(aq) + NH3(aq)

Mention the Bronsted-Lowry acid and base, conjugate pairs of the equation above:

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How to make buffer solutions?
A buffer solution is one which resists changes in pH when small quantities of an acid or an alkali are added to it. Based on the value of pH, buffer is classified
into two kinds of buffer, an acidic buffer solution is simply one which has a pH less than 7 (pH of 4.76), and An alkaline buffer solution has a pH greater than 7 ( pH of 9.25)

a. Acidic buffer solution
Please observe the following data!

No
1 2 3 4

Solutions / mixtures
CH3COOH (aq) + CH3COO- (aq) HCN (aq) + CN- (aq)

The kind of each solution
CH3COOH (aq) = weak acid CH3COO- (aq) = conjugatebase …………………………….. …………………………….. CH3COOH (aq) = weak acid CH3COO- (aq) = the salt of CH3COOH …………………………….. …………………………….. …………………………….. ……………………………..

Acidic buffer / alkaline buffer / not buffer
Acidic buffer Acidic buffer Acidic buffer Not buffer

CH3COOH (aq) + CH3COONa (aq) HCl (aq) + Cl- (aq)

5

HCl (aq)

+ NaCl (aq)

Not buffer

b. Alkaline buffer solution No
1 2 3

Solutions / mixtures
NH3 (aq) NH3 (aq) NaOH(aq) + NH4+(aq) + NH4Cl (aq) + NaCl (aq)

The kind of each solution
…………………………….. …………………………….. …………………………….. …………………………….. …………………………….. ……………………………..

Acidic buffer / alkaline buffer / not buffer
Alkaline buffer Alkaline buffer Not buffer

CONCLUSION
Based on the data above, conclude how to make the acidic buffer solutions and alkaline buffer solutions?

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EXERCISE 1
01. Identify the following mixtures, and classify into acidic buffer solution / alkaline buffer solution / not buffer! a. HCOOH (aq) + HCOO-(aq) b. HCOOH (aq) + (HCOO)2Ca(aq) c. H2SO4(aq) + HSO4-(aq) d. H3PO4(aq) + H2PO4-(aq) e. KOH(aq ) + KCl(aq f. NH3(aq) + (NH4)2SO4(aq)

02. Determine the kind of substance that remains, and classify into acidic buffer solution / alkaline buffer solution / not buffer! a. 100 mL of ethanoic acid solution 0.1M is added into 50 mL of sodium hydrokxide solution 0.1 M. b. 100 mL of ethanoic acid solution 0.1M is added into 50 mL of calcium hydrokxide solution 0.1 M. c. 100 mL of ammonia solution 0.1M is added into 50 mL of sulfuric acid solution 0.1 M. d. 100 mL of ammonia solution 0.1M is added into 50 mL of nitric acid solution 0.1 M.

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This hand out describes simple acidic and alkaline buffer solutions and explains how they work. What is a buffer solution? Definition A buffer solution is one which resists changes in pH when small quantities of an acid or an alkali are added to it. Acidic buffer solutions An acidic buffer solution is simply one which has a pH less than 7. Acidic buffer solutions are commonly made from a weak acid and its conjugate-base or and one of its salts - often a sodium salt, A common example would be a mixture of ethanoic acid and sodium ethanoate in solution. In this case, if the solution contained equal molar concentrations of both the acid and the salt, it would have a pH of 4.76. It wouldn't matter what the concentrations were, as long as they were the same. You can change the pH of the buffer solution by changing the ratio of acid to salt, or by choosing a different acid and one of its salts.

Alkaline buffer solutions An alkaline buffer solution has a pH greater than 7. Alkaline buffer solutions are commonly made from a weak base and its conjugate-acid or and one of its salts. A frequently used example is a mixture of ammonia solution and ammonium chloride solution. If these were mixed in equal molar proportions, the solution would have a pH of 9.25. Again, it doesn't matter what concentrations you choose as long as they are the same. How do buffer solutions work? A buffer solution has to contain things which will remove any hydrogen ions or hydroxide ions that you might add to it - otherwise the pH will change. Acidic and alkaline buffer solutions achieve this in different ways.

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Acidic buffer solutions We'll take a mixture of ethanoic acid and sodium ethanoate as typical. Ethanoic acid is a weak acid, and the position of this equilibrium will be well to the left: Adding sodium ethanoate to this adds lots of extra ethanoate ions. According to Le Chatelier's Principle, that will tip the position of the equilibrium even further to the left. The solution will therefore contain these important things:
• • •

lots of un-ionised ethanoic acid; lots of ethanoate ions from the sodium ethanoate; enough hydrogen ions to make the solution acidic.

Other things (like water and sodium ions) which are present aren't important to the argument. Adding an acid to this buffer solution The buffer solution must remove most of the new hydrogen ions otherwise the pH would drop markedly. Hydrogen ions combine with the ethanoate ions to make ethanoic acid. Although the reaction is reversible, since the ethanoic acid is a weak acid, most of the new hydrogen ions are removed in this way. Since most of the new hydrogen ions are removed, the pH won't change very much - but because of the equilibria involved, it will fall a little bit. Adding an alkali to this buffer solution Alkaline solutions contain hydroxide ions and the buffer solution removes most of these. This time the situation is a bit more complicated because there are two processes which can remove hydroxide ions. Removal by reacting with ethanoic acid The most likely acidic substance which a hydroxide ion is going to collide with is an ethanoic acid molecule. They will react to form ethanoate ions and water.

Because most of the new hydroxide ions are removed, the pH doesn't increase very much.

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Removal of the hydroxide ions by reacting with hydrogen ions Remember that there are some hydrogen ions present from the ionisation of the ethanoic acid. Hydroxide ions can combine with these to make water. As soon as this happens, the equilibrium tips to replace them. This keeps on happening until most of the hydroxide ions are removed.

Again, because you have equilibria involved, not all of the hydroxide ions are removed - just most of them. The water formed re-ionises to a very small extent to give a few hydrogen ions and hydroxide ions. Alkaline buffer solutions We'll take a mixture of ammonia and ammonium chloride solutions as typical. Ammonia is a weak base, and the position of this equilibrium will be well to the left:

Adding ammonium chloride to this adds lots of extra ammonium ions. According to Le Chatelier's Principle, that will tip the position of the equilibrium even further to the left. The solution will therefore contain these important things:
• • •

lots of unreacted ammonia; lots of ammonium ions from the ammonium chloride; enough hydroxide ions to make the solution alkaline.

Other things (like water and chloride ions) which are present aren't important to the argument. Adding an acid to this buffer solution There are two processes which can remove the hydrogen ions that you are adding. Removal by reacting with ammonia

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The most likely basic substance which a hydrogen ion is going to collide with is an ammonia molecule. They will react to form ammonium ions.

Most, but not all, of the hydrogen ions will be removed. The ammonium ion is weakly acidic, and so some of the hydrogen ions will be released again. Removal of the hydrogen ions by reacting with hydroxide ions Remember that there are some hydroxide ions present from the reaction between the ammonia and the water.

Hydrogen ions can combine with these hydroxide ions to make water. As soon as this happens, the equilibrium tips to replace the hydroxide ions. This keeps on happening until most of the hydrogen ions are removed.

Again, because you have equilibria involved, not all of the hydrogen ions are removed - just most of them. Adding an alkali to this buffer solution The hydroxide ions from the alkali are removed by a simple reaction with ammonium ions.

Because the ammonia formed is a weak base, it can react with the water - and so the reaction is slightly reversible. That means that, again, most (but not all) of the the hydroxide ions are removed from the solution.

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(worksheet 2nd)
Drs. M. Hariyanto SMA Negeri 3 Malang (Public Senior High School) Jl. Sultan Agung Utara No 7 Phone (0341) 324 768 Malang 65111 (web site : http://www.har-chemist.co.nr )

Calculate [H+] and [OH-] in buffer solutions
pH of buffer solutions can be determined by using acid-base indicators or by calculating of concentration of hudrogen ion or hydroxide ion.The components of buffer solutions are weak acid and its conjugate-base (acidic buffer) or weak base and its conjugate-acid (alkaline buffer), so what is the relationship between [H+] and the acid dissociation constant (Ka) or [OH-] and the base dissociation constant (Kb). In the next activity you will be understand the both relationships..

1. The acidic buffer solutions No Steps
1 The acidic buffer solution consists weak acid HA and its salt LA. Write the ionization of each substance in water! Write the formulae of Ka of HA from reaction 1a

Solutions
Ionizations : HA (aq) ↔ ….(aq) + …(aq) (1a) LA (aq)→ …..(aq) +… (aq) (1b)

2

Ka = ……………………

(2)

3

The adding of A- ion from salt, LA can shift the equilibrium system of HA to the left ( ractants), so [A-] from ionization of HA is decreasing. The number of [A-] [H+] = ………………………..(3) from salt, LA in system are greater extremely than [A-] from HA . The [A-] in solutions that contribute in calculation are only the quantity of [A-] from salt. Write the relation between [H+], Ka, [HA] and [A-]. Where : Ka = The acid dissociation constant [HA] = concentration of weak acid [A-] = concentration of conjugate-base / anion of salt

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2. The alkaline buffer solution No Steps
1 The acidic buffer solution consists weak base MOH and its salt MA. Write the ionization of each substance in water! Write the formulae of Kb of MOH from reaction 1a

Solutions
Ionizations : MOH(aq) ↔ ….(aq) + …(aq) (1a) MA (aq)→ …..(aq) +… (aq) (1b)

2

Kb = ……………………

(2)

3

The adding of M+ ion from salt, MA can shift the equilibrium system of MOH to the left ( ractants), so [M+] from ionization of MOH is decreasing. The number of [H+] = ………………………..(3) [M+] from salt, MA in system are greater extremely than [M+] from MOH . The [M+] in solutions that contribute in calculation are only the quantity of [M+] from salt. Write the relation between [OH-], Kb, [MOH] and [M+]. Where : Kb = The base dissociation constant [MOH] = concentration of weak base [M+] = concentration of conjugate-acid / cation of salt

Conclusion

Notes

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1. Write the formulae of [H+] of the following buffer solutions: a. The mixture of HCOOH and HCOONa aqueous solution b. The mixture of HCN and Ca(CN)2 aqueous solution

2. Write the formulae of [H+] of the following buffer solutions: a. The mixture of NH3 and NH4+ aqueous solution b. The mixture of NH3 and (NH4)2SO4 aqueous solution

3. Calculate the pH of 600 mL of HCN 0.01 M dand 100 mL of KCN 0.01 M, given that Ka HF = 6 x 10-4

4. Calculate the pH of 100 mL of HF 0,06 M and 100 mL of BaF2 0.01 M, given that Ka HF = 6 x 10-4

5. Determine the pH of 180 mL of NH3 0.01 M and 100 mL ofNH4NO3 0.01 M , given that Kb NH3 = 1.8 x 10-5

6. Determine the pH of 200 mL of NH3 0.01 M and 90 mL of (NH4)2SO4 0.01 M, given that Kb NH3 = 1.8 x 10-5

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7. What is the volume of acetic acid 0,01M must be added into 200 mL of sodium acetic 0.1M to form the buffer solution that has pH = 5. Given that Ka CH3COOH = 1 x 10-5

8. How many grams of ammonium chloride (Mr = 53,5) must be added into 200 mL of ammonia 0,1M to form the buffer solution that has pH = 9. Given thatKb NH3 = 1 x 10-5

9. Determine the proportion of volume of H2CO3 0.01 M and HCO3- 0.5 M to form the buffer solution that has pH = 6 – log 5 (Ka H2CO3 = 5 x 10-7)

10. Calculate the pH of 200 mL larutan HF 0.1 M and 100 mL of Ba(OH)2 0.025 M. Given that Ka HF = 6 x 10-4

11. Calculate the pH of 200 mL of NH3 0.1 M and 100 mL of HCl 0.1M. Given that Kb NH3 = 1 x 10-5

12. How many grams of NaOH powder (Mr = 40) must be added into 500 mL of acetic acid 0.1 M to form the buffer that has pH = 5. Ka CH3COOH = 1 x 10-5

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13. How many drops of calcium hydroxide 1 M must be dropped and dropped into 100 mL of acetic acid 0.01 M to form the buffer that has pH= 5 - log 9 . (Ka CH3COOH = 1 x 10-5)

14. How many dropps of sulfuric acid 1 M must be dropped and dropped intoharus 100 mL of ammonia 0.01 M to form the buffer that has pH-nya 9 + log 9 (Kb NH3 = 1 x 10-5)

15. One liter of the buffer solution that made from barium hydroxide aqueous solution 0.1 M and hydrofluoric acid 0.1 M has pH = 4 – log 6. When Ka HF = 6 x 10-4, determine the volume of each solution in the initial mixture.

16. Five hundreds milliliters of buffer solution that made from amonia 0.1 M and sulfuric acid 0.1 M has pH = 9. If Kb NH3 = 1 x 10-5, determine the volume of each solution in the initial mixture.

17. Five hundreds milliliters of buffer solution that made from amonia 0.1 M and sulfuric acid 0.1 M has pH = 9 - log 6. If Kb NH3 = 1 x 10-5, a. determine the volume of each solution in the initial mixture. b. Determine the pH after the buffer is added by 50 mL of sulfuric acid 0.2 M

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(worksheet 3rd)
Drs. M. Hariyanto SMA Negeri 3 Malang (Public Senior High School) Jl. Sultan Agung Utara No 7 Phone (0341) 324 768 Malang 65111 (web site : http://www.har-chemist.co.nr )

Adding an acid and an alkali to buffer solutions
Purposes :
Students are able to
1) explain the effect of adding a little acid to buffer solution 2) explain the effect of adding a little alkali to buffer solution

Material and aparattus
No 1 2 3 4 5 6 7 8 9 10 11 Material /aparattus Reaction tube Silinder ukur Pipette HCl (aq) NaOH (aq) CH3COOH (aq) CH3COONa (aq) NH3 (aq) NH4Cl (aq) Aquadest Universal indicator Size 10 mL 0.1 M 0.1 M 0.1 M 0.1 M 0.1 M 0.1 M Quantity 11 / 1 1 8 25 mL 25 mL 3 mL 3 mL 3 mL 3 mL -

Procedure
PART I 1. Prepare 2 pieces of clean reaction tube 2. Pour to each tube above, 2 mL of hydrochloric acid 0.1 M and 2 dropps of universal indicator, and measure its pH. 3. Do the following experiments : a. Into the first tube (1.1), add dropp by dropp the solution of NaOH 0.1 M until the colour changes. Write the number of dropp and pH. b. Into the second tube (1.2), dilute two times by adding 2 mL of aquadest, observe its colour!, if the colour has not changed, dilute 3 times by adding 2 mL of aquadest , etc until the colour changes. Write the volume of adding aquadest and its pH. PART II 1. Prepare 2 pieces of clean reaction tube 2. Pour to each tube above, 2 mL of sodium hydroxide 0.1 M and 2 dropps of universal indicator, and measure its pH. 3. Do the following experiments : a. Into the first tube (1.1), add dropp by dropp the solution of HCl 0.1 M until the colour changes. Write the number of dropp and pH.

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b. Into the second tube (1.2), dilute two times by adding 2 mL of aquadest, observe its colour!, if the colour has not changed, dilute 3 times by adding 2 mL of aquadest , etc until the colour changes. Write the volume of adding aquadest and its pH. PART III 1. Prepare 3 pieces of clean reaction tube 2. Pour to each tube above, the mixture of 1 mL of acetic acid 0.1 M and 1 mL of sodium acetic 0.1 M, then add 2 dropps of universal indicator, and measure its pH. 3. Do the following experiments : a. Into the first tube (1.1), add dropp by dropp the solution of HCl 0.1 M until the colour changes. Write the number of dropp and pH. b. Into the first tube (1.2), add dropp by dropp the solution of NaOH 0.1 M until the colour changes. Write the number of dropp and pH. c. Into the second tube (1.3), dilute two times by adding 2 mL of aquadest, observe its colour!, if the colour has not changed, dilute 3 times by adding 2 mL of aquadest , etc until the colour changes. Write the volume of adding aquadest and its pH. PART III 1. Prepare 3 pieces of clean reaction tube 2. Pour to each tube above, the mixture of 1 mL of ammonia 0.1 M and 1 mL of ammonium chloride 0.1 M, then add 2 dropps of universal indicator, and measure its pH. 3. Do the following experiments : a. Into the first tube (1.1), add dropp by dropp the solution of HCl 0.1 M until the colour changes. Write the number of dropp and pH. b. Into the first tube (1.2), add dropp by dropp the solution of NaOH 0.1 M until the colour changes. Write the number of dropp and pH. c. Into the second tube (1.3), dilute two times by adding 2 mL of aquadest, observe its colour!, if the colour has not changed, dilute 3 times by adding 2 mL of aquadest , etc until the colour changes. Write the volume of adding aquadest and its pH.

Observation result
PART I : 2 mL of HCl 0.1 M is added by NaOH 0.1 M and diluted The solution Volume colour pH change that added dropps / initial after initial after mL NaOH 0.1 M Aquadest PART II : 2 mL of NaOH 0.1 M is added by HCl 0.1 M and diluted The solution Volume colour pH change that added dropps / initial after initial after mL HCl 0.1 M Aquadest

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PART III: 1 mL of CH3COOH 0.1 M and 1 mL of CH3COONa 0.1 M are added by HCl 0.1 M, NaOH 0.1 M and diluted The solution Volume colour pH change that added dropps / initial after initial after mL HCl 0.1 M NaOH 0.1 M Aquadest PART IV: 1 mL of NH30.1 M and 1 mL of NH4Cl 0.1 M are added by HCl 0.1 M, NaOH 0.1 M and diluted The solution Volume colour pH change that added dropps / initial after initial after mL HCl 0.1 M NaOH 0.1 M Aquadest

Assignments
Based on the data above, plot the graph of volume versus the pH changes. ADDING AN ACID
NaOH 0.1 M An acidic buffer solution An alkaline buffer solution pH
14 13 12 11 10 9 8 7 6 5 4 3 2 1 Volume of HCl 0.1 M Volume of HCl 0.1 M Volume of HCl 0.1 M

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ADDING AN ALKALI
HCl 0.1 M An acidic buffer solution An alkaline buffer solution pH
14 13 12 11 10 9 8 7 6 5 4 3 2 1 Volume of NaOH 0.1 M Volume of NaOH 0.1 M Volume of NaOH 0.1 M

DILUTION
HCl 0.1 M NaOH 0.1 M Acidic buffer alkaline buffer pH
14 13 12 11 10 9 8 7 6 5 4 3 2 1 Volume of H2O Volume of H2O Volume of H2O Volume of H2O

Conclusion
Based on the slope of the graph above , conclude the effect of adding a little acid, a little alkali and dilution to the change of pH of an acid, an alkali, an acidic buffer, and an alkaline buffer solution.

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(worksheet 1st)
Drs. M. Hariyanto SMA Negeri 3 Malang (Public Senior High School ) Jl. Sultan Agung Utara No. 7 Telp (0341) 324768 Malang 65111

(Web site : http://www.har-chemist.co.nr )

salt, the reaction of salt formation, the kind of salt based on the parent acid and parent base that react to produce salt.

Before we study about hydrolysis of salt, we should review about definition of

Discuss the following questions! No
1 2 3

Questions
Based on the chemical formula of salt, mention the components of salt! Based on the reaction of salt formation , what are the substances that react to produce the salt? Based on the strength of acid and base that combine ( the parent acid and parent base), mention the kind of salt! Give the example of salt, based on the question no 3!

answer
………………………………………. ………………………………………. ………………………………………. ………………………………………. ………………………………………. ………………………………………. ………………………………………. ………………………………………. ………………………………………. ……………………………………….

4

MEASURING OF THE pH OF SALTS
PURPOSES
1) measure the pH of salts by experiments strength of acid and base that combine Students are able to :

2) conclude the relation between the pH of salt and the kind of salt based on the

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MATERIAL AND APARATTUS No Material / aparattus
1 2 3 4 5 6 7 8 9 10 palette pipette NaCl (aq) Na2CO3(aq) CH3COONa(aq) NH4Cl(aq) Al2(SO4)3(aq) Ba(NO3)2(aq) Litmus ( red and blue) Universal indicator

Measure
1M 1M 1M 1M 1M 1M -

Quantity
1 6 2 mL 2 mL 2 mL 2 mL 2 mL 2 mL 6 6

1. Drop the solution of each salt to palette about 3 dropps 2. Test by litmus and observe the colour change of litmus 3. Measure the pH of salt solution by universal indicator

PROCEDURE

OBSERVATION RESULT
nO 1 2 3 4 5 6 SOLUTIONS NaCl (aq) Na2CO3(aq) CH3COONa(aq) NH4Cl(aq) Al2(SO4)3(aq) Ba(NO3)2(aq) THE COLOUR CHANGES OF RED LITMUS ……………… ……………… ……………… ……………… ……………… ……………… RED LITMUS ……………… ……………… ……………… ……………… ……………… ……………… ………… ………… ………… ………… ………… ………… pH ACIDIC / BASIC / NEUTRAL ……………… ……………… ……………… ……………… ……………… ………………

QUESTIONS nO
1

QUESTIONS
Based on the experiments above, mention the properties of each salt solution, acidic / alkaline or neutral

ANSWER
…………………………………… …………………………………… …………………………………… …………………………………… …………………………………… …………………………………… …………………………………… ……………………………………

2

If the salts that hydrolized in water are not the neutral salts, mention which are the salts that hydrolized in the experiment above!

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4. Complete the following table!

No

Solution

The parent base Chemical formulae Strong / weak

The parent acid Chemical formulae Strong / weak

1 2 3 4 5 6

NaCl (aq) Na2CO3(aq) CH3COONa(aq) NH4Cl(aq) Al2(SO4)3(aq) Ba(NO3)2(aq)

1. The kind of salt based on the strength of parent acid and parent base
No
1 2 3 4 2. The kind of salts that hydrolized in water are : ……………………………………………………….. ……………………………………………………….. ………………………………………………………..

CONCLUSION

The strength of The parent base The parent acid

The property of salt ( acidic / basic / neutral)

1. Complete the following table!

No

Solution

The Parent Base of salt Chemical formulae Strong / weak

The Parent Acid of salt Chemical formulae Strong / weak

1 2 3 4 5 6

NaNO3 (aq) Ba(CH3 COO)2 (aq) (NH4)2SO4 (aq) NH4CN(aq) KI(aq) CaS(aq)

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2. The following salts, hydrolized or not in water? Explain! a. Sr(ClO4)2 b. NaF c. NH4Br

d. CH3COONH4

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Hydrolysis Reactions
A salt of a strong acid and a strong base (such as NaCl from HCl and NaOH) produces a neutral solution when dissolved in water. However, when a salt of a weak acid and a strong base (e.g. NaAc from acetic acid and NaOH), a strong acid and a weak base (e.g. NH4Cl from ammonia and HCl), or a weak acid and a weak base (NH4Ac) is dissolved in water, the solution does not have a neutral pH. These phenomena are explained by the reaction of the salts of weak acids and weak bases with water in hydrolysis reactions. As shown in Figure 2.1, these hydrolysis reactions produce the parent weak acids and weak bases of the salts:

Figure 2.1: Hydrolysis reactions

As you can see in the figure above, the salt of a weak acid, such as acetate ion, acts as a base in water, and the salt of a weak base, such as ammonium ion, acts as a weak acid. From our previous discussion on the reactions of acids and bases with water in Disassociations, you should know that the Kb of acetate ion can be calculated from the Ka of acetic acid, and that the Ka of ammonium ion can be calculated from the Kb of ammonia, as shown in figure 2.1. Another type of hydrolysis reaction comes from the reaction of metal ions with high charges. Such ions act as Lewis acids to water molecules, as shown in Figure 2.2. A metal ion can bond to water by accepting an lone pair from the oxygen of a water molecule, and this increases the acidity of water molecule. Like other acids, we can calculate the Ka and calculate the pH of a solution containing such ions.

Figure 2.2: Why metal ions decrease the pH of aqueous solutions

To calculate the pH of a solution containing the salt of a weak acid or a weak base, treat the problem exactly as you did when calculating the pH of weak acid and base solutions above in Calculating pH's, Heading . Mixtures of salts of weak acids and weak bases present a challenging mathematical problem that we will not cover in our treatment of acid-base chemistry.

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Terms

Acid - A substance that has the potential to donate a proton or accept an electron pair. Acidic - Having a pH less than 7 or a pOH greater than 7. Base - A substance that can accept a proton, release OH-, or donate an electron pair. Basic - Having a pH greater than 7 or a pOH less than 7. Hydrolysis - A reaction that modifies a water molecule. In acid-base chemistry this usually refers to the reaction of a solute which changes the pH of an aqueous solution. Parent acid - An acid that reacts with base to produce the salt Parent base - A base that reacts with acid to produce the salt pH - A measure of the hydrogen ion concentration, it is equal to - log [H+]. pKa - A measure of the strength of an acid, it is equal to - log Ka, where Ka is the acid dissociation constant in water. pKb - A measure of the strength of a base, it is equal to log Kb, where Kb is the base dissociation constant in water. pOH - A measure of the hydroxide ion concentration, it is equal to - log [OH- ]. Strong Acid - An acid with a pKa less than zero. Strong acids completely dissociate in water. Strong Base - A base with a pKb less than zero. Strong bases completely dissociate in water. Weak Acid - An acid with a pKa greater than zero. Weak acids do not completely dissociate in water. Weak Base - A basewith a pKb greater than zero. Weak bases do not completely dissociate in water.

Weakness of attitude become weakness of character (Albert Einstein)

Worksheet of chemistry/xi krsnbi/ by m. hariyanto

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(worksheet 2nd)
Drs. M. Hariyanto SMA Negeri 3 Malang (Public Senior High School ) Jl. Sultan Agung Utara No. 7 Telp (0341) 324768 Malang 65111

(Web site : http://www.har-chemist.co.nr )

Determaining [OH-] or [H+] of hydrolyzed salt solutions
The pH of salt solutions can be measured by universal indicator, also can be determained by calculation. In the previous activity, we have concluded that the salts from strong base and acid are not hydrolyzed, so their pH equal with water’s pH (neutral). But the other salts ( from weak base-strong acid or strong base-weak acid) are hydrolyzed, so their property are acidic, or basic.

How to calculate the pH of salt solution?
In the next activity, you will determain the relation among hydrolysis constant (Kh), dissociation constant of water (Kw), [OH-] or [H+] in the salt solutions

1. THE SALT FROM THE STRONG BASE (LOH) AND STRONG ACID (HZ) No Questions Solution
1 2 3 4 5 The chemical formulae of salt Ionization in water Hydrolysis in water Hydrolysis constant (Kh) The value of [H+] LZ LZ → ......... + ............ (cation of strong base) (anion of strong acid) Not hydrolyzed Doesn’t have Kh [H+] = [H+] in water =

Kw

2. THE SALT FROM STRONG BASE (LOH) AND WEAK ACID (HA) No
1 2 3

Questions
The chemical formulae of salt Ionization in water Hydrolysis in water (the weak ion) The hydrolysis constant (Kh) a. The hydrolysis constant of A- ion ( reaction 2) LA LA → .........

Solution
(1) + ............ (2)
(cation of strong base) (anion of weak acid)

A- (aq)+H2O (l) ↔HA(aq) + OH-(aq) (3) Produced OH- ion in solution causes the property of salt :............ (acidic/basic/neutral) a. The hydrolysis constant of A- ion K = ............................. (4a)

4

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b. From the formulae of Ka (question 4a), the value of [H2O] doesn’t change, so K.[H2O] can be expressed by Kh 5 The relation among Kh, Kw and Ka a. Write the formulae of Kw b. Write ionization of weak acid, HA and write theformulae of its Ka

b. If K.[H2O] is expressed by Kh, so : Kh = ............................. (4b)

a. Ionization of water : H2O ↔ ........ + ........ Kw = ........................ (5a) b. HA ↔ ........ + .......... Ka =...........................

c. The formulae of Kh (4b), multiply by :

[H ] [H + ]
d. Substitute Kw and 1/Ka to equation (5c) above, so you will get the formulae of Kh of salt from strong base and weak acid. 5 The value of [OH-] Please observe the hydrolysis of A – ion that [HA] = [OH-], so the multiplication of [HA]. [OH-] expressed by [OH-]2. Substitute this equation the formulae of Kh (equation 4b)

+

1 = ............................. Ka
c. Kh = ..........................

(5b) (5c)

d. Kh = ............................

(5d)

Kh =........................ [OH-]2 = ................... [OH-] = ............ (6)

3. THE SALT FROM WEAK BASE (MOH) AND STRONG ACID (HZ) No Pertanyaan The chemical formulae of salt 1 2 3
Ionization in water Hydrolysis in water (the weak ion) The hydrolysis constant (Kh) c. The hydrolysis constant of A- ion ( reaction 2) d. From the formulae of Ka (question 4a), the value of [H2O] doesn’t change, so K.[H2O] can be expressed by Kh The relation among Kh, Kw and Ka a. Write the formulae of Kw b. Write ionization of weak acid, HA and write theformulae of its Ka

Penyelesaian MZ MZ → ......... + ............
(Cation of weak base (anion of strong acid)

(1) (2)

M+ (aq)+H2O (l) ↔MOH(aq) + H+(aq) (3) Produced H+ ion in solution causes the property of salt :............ (acidic/basic/neutral) a. The hydrolysis of constant of M+ ion K = ............................. b. If K.[H2O] expressed by Kh, so : Kh = ............................. (4b) (4a)

4

5

a. Ionization of water : H2O ↔ ........ + ........ Kw = ........................ (5a) b. MOH ↔ ........ + .......... Kb =...........................

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c. The formulae of Kh (4b), multiply by :

[OH ] [OH − ]
d. Substitute Kw and 1/Kb to equation (5c) above, so you will get the formulae of Kh of salt from weak base and strong acid.

1 = ............................. Kb
c. Kh = .......................... d. Kh = ............................

(5b) (5c) (5d)

6

The value of [OH-] Please observe the hydrolysis of M+ ion that [MOH] = [H+], so the multiplication of [MOH]. [H+] expressed by [H+]2. Substitute this equation the formulae of Kh (equation 4b)

Kh =........................ [H+]2 = ................... [H+] = ............ (6)

4. THE SALT FROM WEAK BASE (MOH) AND WEAK ACID (HA) No Questions Solution
1 2 3 The chemical formulae of salt Ionization in water Hydrolysis in water (the weak ion ) MA MA → ......... + ............
(cation of weak base) (anion of weak acid)

(1) (2)

M+ (aq)+H2O (l) ↔MOH(aq) + H+(aq) A- (aq)+H2O (l) ↔HA(aq) + OH-(aq) M+ + A- +H2O ↔ MOH + HA

+ (3)

4

The hydrolysis constant (Kh) a. Write the equilibrium constant ionization of M+ (reaction 2) dan b. From the formulae of K question 4a, the value of [H2O] doesn’t change, so K.[H2O] can be expressed by Kh The relation among Kh, Kw and Kb a. Write the formulae of Kw, 1/Ka, dan 1/Kb

a. The equilibrium constant of reaction (3) K = ............................. (4a)

b. If K.[H2O] can be expressed by Kh, so : Kh = ............................. a. Kw = ........................ (4b) (5a1) (5a2) (5a3) (5b)

5

b. The formulae of Kh (4b), multiply by

1 = ............................. Kb 1 = ........................... Ka
b. Kh = ..........................

[ H + ].[OH − ] [ H + ].[OH − ]
c. Substitute Kw ,1/Kb, and 1/Ka to equation (5b) above, so you will get the formulae of of salt from weak base and weak acid. The value of[H+] Observe the hydrolysis of A- ion and M+ ion that [MOH] = [HA], and [A-] = [M+], c. Kh = ............................ (5c)

6

Kh =

[ MOH ].[ HA] [ M + ].[ A − ]

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so [MOH]. [HA]= [HA]2 and [M+].[A-] = [A-]2 Substitute this equation to the formula of Kh (equation 4b) Then multiply by:

[ H + ]2 [ H + ]2

[ HA] 2 [ H + ] 2 x [ A − ]2 [ H + ]2 1 Kh = .[ H + ] 2 2 Ka + [H ] = ............
=

(6)

Questions
No
1

Questions
Based on the the strength of parent base and parent acid, clasify the kind of salt and give 1 example of each salt! Write the hydrolysis reaction of salt in number 1. Based on the kind of cation and anion that hydrolyzed, mention the kind of hydrolysis .

Answer
................................................................. ................................................................. ................................................................. ................................................................. ................................................................. ................................................................. ................................................................. ................................................................. .................................................................

2

3

Conclusion
Salts Partial hydrolyzed/ Total hydrolyzed/ not hydrolyzed Kh [H+] or [OH-] Property (acidic/basic/ neutral) Notes

SB-SA

Not hydrolyzed

-

[H+]=

Kw

neutral

SB-WA

[A-] = concentration anion of salt [M+] = concentration of cation of salt

WB-SA

WB-WA

SB = strong base SA = strong acid WB = weak base WS = weak acid

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1. The solution of Fe2(SO4)3 . a. Mention the parent base and acid b. Write the hydrolysis reaction c. What is the property of salt (acidic/basic/neutral)

2. Calculate the pH of the following salts : a. 200 mL of (CH3COO)2 Ca 0.05 M (Kh NaAc = 10- 9) b. 200 mL of (NH4)2 SO4 0.0005 M (Kb NH3 = 10- 5) c. 200 mL CH3COONH4 0,173M (Kb NH3 = 10- 5 and Ka CH3COOH = 10- 5)

3. The mixture of 50 mL of NH4OH 0.1 M + 50 mL of HCl 0.1 M ,Calculate the pH of before and after mixed. Kb amonia = 10-

5

4. The mixture 50 mL of Ba(OH)2 0.1 M + 100 mL of HCN 0.1M,Calculate the pH of before and after mixed . Ka HCN = 10- 7

5. The mixture 50 mL of H2SO4 0.1 M + 100 mL of NH3 0.1 M ,calculate the pH before and after mixed. Kb NH3 = 10- 5

PREDICTION IS VERY DIFFICULT, ESPECIALLY ABOUT THE FUTURE (NIELS BOHR)

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Worksheet 1st
Drs. M. Hariyanto SMA Negeri 3 Malang (Public Senior High School) Jl. Sultan Agung Utara No 7 Phone (0341) 324 768 Malang 65111 (web site : http://www.har-chemist.co.nr )

Although all compounds have a characteristic solubility in water at a given temperature, some families of compounds are more soluble than others and it is useful to know certain general rules of solubility. We call any substance the solubility of which is less than 0.01 mol/L insoluble. If its solubility is greater than 0.1 mol/L, we call it soluble. If its solubility is between 0.01 and 0.1 mol/L, we say that it is slightly soluble. The following solubility rules can be used to determine solubilities in water, with the disclaimer that they don't always hold, nor do they include every ion which is in common use, but they are good to have nearby when needed: 1. All sodium, potassium, and ammonium salts are soluble. 2. All nitrates, acetates and perchlorates are soluble. 3. All silver, lead and mercury(I) salts are insoluble. 4. All chlorides, bromides and iodides are soluble. 5. All carbonates, sulfides, oxides and hydroxides are insoluble. 6. All sulfates are soluble except calcium sulfate and barium sulfate.

A. Solubility
1. Definition of solubilty
Complete the following table! The amount of substance in water 15 grams of P 25 moles of Q 10 grams of R 5 moles of S The amount of dissolved in water 3 grams 0,2 moles 0,04 mgrams 0,01 moles Volume of solvent ( dm3) 10 20 1 4 solubility 0,3 gram/dm3 ................. ................ ................

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Questions
Based on the data above, answer the following questions! No Questions answer 1 What is solubility? ........................................................... 2 3 What is the unit of solubility? Write the equation of relationship among solubility (s), number of mole of solute (n), and volume of solvent (V) ........................................................... ........................................................... ...........................................................

2. The factors that influence the value of solubility of substance in water
What are the factors that influence the value of solubility? Observe the following data, and answer the questions!

The amount of substance
10 grams of A 10 grams of B

The solubility at 25oC
0,1 g/dm 0,05 g / dm3
3

The solubility in solvent
0,15 g/dm3 0,2 g/dm3

0,2 g/dm3 0,075 g/dm3

50oC

water

0,1 g/dm3 0,3 g/dm3

Alcohol

Questions
Based on the data above, answer the following questions! No Questions Answer .......................................................... 1 Based on the data above, what are the factors that influence the value of .......................................................... .......................................................... solubility of substance in water?

1. If the solubility of BaSO4 in water is 1 x 10-5 mol/L, determine the solubility of BaSO4 by unit mg/L (Mr BaSO4 = 233)

2. The solubility of Mg(OH)2 in water is 2 x 10-4 M, how many grams of Mg(OH)2 that can soluble in 500 mL of water ( Mr Mg(OH)2=58)

3. The maximum mass of L2X3 (Mr=100) that can dissolve in 200 mL of water is 5 x 10-3 mg. Calculate the solubility of L2X3 in water by unit moles/L

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B. Solubility Product Constant (Ksp)

Expression of Ksp
Before you write the expression of Ksp (solubility product constant) of saturated substance, answer the following questions!

No
1 2 3

Questions
Ag2CrO4 is the saturated substance, Write the ionization of Ag2CrO4 in water! Write the equilibrium constant (K) of equation no 1 If the equilibrium constant of saturated substance is expressed by Ksp, write the Ksp of Ag2CrO4!

Answer
Ag2CrO4(s) ↔ .......(aq) + ........(aq)

K = ................................................ Ksp Ag2CrO4 = .................................

Individual assignments
Fill the blank ! NO The chemical formulae
1 2 3 4 5 6 7 8 9 10 AgCl CaCO3 Ag2S Fe(OH)3 CuCl2 Al2(SO4)3 PbCl2 BaSO4 Al(OH)3 BaF2

The equilibrium equation
AgCl(s) ↔ Ag+(aq) + Cl-(aq)

The formulae of Ksp
Ksp=[Ag+][Cl-]

Conclusion
If the saturated substance is symbolized by LxAy, Write the ionization equation and its Ksp expression

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The relation between Ksp and the solubility of substance in water (s)
Individual assignments
No 1 2 3 Questions If the saturated substance is symbolized by LxAy, Write the ionization equation If the concentration of LxAy equal with its solubility (= s), determine the [Ly+] and [Ax-] by using coefficient ratio! Write the formulae of Ksp of LxAy, and substitute the value of [Ly+] and[Ax-] from equation no 2, so you get the relationship between Ksp and s. Where: s = solubility of substance in water; x = the coefficient of cation; y = the coefficient of naion Answer LxAy(s) ↔ ........(aq) + .......(aq) LxAy(s) ↔ ........(aq) + .......(aq) s ~ ........... ~ ......... Ksp LxAy = ........................

or s = .............................

1. Write the relationship between Ksp and s. NO The chemical formulae
1 2 3 4 5 6 7 8 9 10 AgCl CaCO3 Ag2S Fe(OH)3 CuCl2 Al2(SO4)3 PbCl2 BaSO4 Al(OH)3 BaF2

The formulae of Ksp
Ksp=[Ag+][Cl-] = s2

The formulae of (S)
s = √Ksp

2.Calculate the Ksp of CuCl2 , if its solubility in water is 10-3M

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3. Calculate the solubility of Ag2CrO4(s) , given that Ksp = 2,4 .10-12

4. Determine the Ksp of AgCl, if the solubility of AgCl in water = 0,7175 mg/500 mL

5. How many miligrams of Ag3PO4 (Mr=419) that can soluble in 500 mL of water, given that its Ksp = 2,7 x 10-11?

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Worksheet 2nd
Drs. M. Hariyanto SMA Negeri 3 Malang (Public Senior High School) Jl. Sultan Agung Utara No 7 Phone (0341) 324 768 Malang 65111 (web site : http://www.har-chemist.co.nr )

Precipitation reaction
When we mix two electrolytes substances that by theorytically produce precipitation, but in facts we will get 3 possibility of products; no precipitation occurs (unsaturated), will have precipitated (saturated) or produce precipitation (supersaturated) Why these are happened? Observe the following data! And complete it!
No Substance The concentration of ions in solution
[Ag+] = 10-6 M [Br-] = 10-7 M Ag+] = 10-5 M [Br-] = 10-7 M Ag+] = 2. 10-6 M [Br-] = 2. 10-7 M [Mg2+] = 10-6 M [OH-] = 10-4 M [Mg2+] = 10-5 M [OH-] = 10-2 M [Mg2+] = 2.10-6 M [OH-] = 2.10-3 M

1

AgBr

[Ag+].[Br-]= 10-13 [Ag+].[Br-]= 10-12

The product of concentration of ions or Trial product (Qc)

Ksp

Precipitation

4 x 10-13

[Ag+].[Br-]= 4. 10-13 ............................ ............................ ............................. 8 x 10-12

2

Mg(OH)2

AgBr has not precipitated (unsaturated) AgBr has precipitated (supersaturated) AgBr will have precipitated (saturated) ............................ ............................ .............................

Conclusion
Based on the data , conclude the relation among Qc, Ksp and the forming of precipitation!

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Example
1. Ksp for PbCl2 = 6,25 .10– 5, should precipitation occurs if 100 mL of Pb(NO3)2 0.005 M is mixed with 100 mL of HCl 0.005 M Solution : The number of mole of Pb(NO3)2 = 100 x 0.005 = 5 mmoles The number of mole of HCl = 100 . 0,005 = 5 mmoles + 2 NO3PbCl2 → Pb2+ 5 mmoles ∼ 5 mmoles ∼ 10 mmoles HCl → H+ + Cl5 mmoles ∼ 5 mmoles ∼ 5 mmoles Concentration of each ion after mixed. [Pb2+] = 5 mmoles /200 ml = 2.5 x 10-2 M [Cl- ] = 5 mmoles /200 ml = 2.5 x10-2 M The trial product or Qc of PbCl2 = [Pb2+] [Cl- ]2 =(2.5 x10-2)( 2.5 x10-2)2 = ………… Qc (> / < / = ) Ksp , so ……………………………..

1. One hundred mililitres of the saturated solution of BaF2 , contains 17.5 mg of precipitation after evaporated. Determine the Ksp for BaF2 , given that the relative atomic mass of Ba and F are 137 and 19.

2.How many grams of Al2(SO4 )3 that can dissolve in 250 mL of solution , if Ksp for Al2(SO4)3 = 3,2 . 10-34.(Ar Al = 27; O = 16 ; S = 32.)

3. Calculate the pH of the saturated solution of Al(OH)3 , if Ksp for Al(OH)3 = 1,6. 10-35.

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4.The pH of saturated solution of Zn(OH)2 is 8, determine Ksp for Zn(OH)2.

5. Should precipitation occurs of BaSO4 ,If 200 mL of Ba(NO3)2 0.025 M is mixed with 300 mL of Na2SO4 0.05 M. ( Ksp for BaSO4 = 1.5 x 10-9)

6.The solution of FeBr3 0.2 M is dropped by NH3 solution, determine the pH when start precipitation of Fe(OH)3, Ksp for Fe(OH)3 = 1.6 x 10-36 ( assume that the volume of mixture doesn’t change by ammonia addition)

7. Ksp forBaSO4 = 1 x 10-10. If barium hydroxide that its pH= 11 is mixed with sulfuric acid that its pH = 3 so the volume of mixture 1 Litre. a. predict ! Should precipitation occurs? b. if precipitation occurs, calculate the mass of BaSO4 that precipited (Mr=233) c. calculate the concentration of Ba2+ and SO42- in solution!.

8. One litre of MgCl2 0.0001 M is added drop by drop with KOH 2 M, if Ksp for Mg(OH)2 = 9 x 10-12, how many drops of KOH required to start precipitation of Mg(OH)2 ?

9. Gived that Ksp for BaSO4 = 1 x 10-10, Ksp for MgSO4 = 1 x 10-5, Ksp for SrSO4 = 3 x 10-7 and Ksp for CaSO4 = 3 x 10-6. If into the 500 mL of the mixture of BaCl2, MgCl2, SrCl2 andCaCl2 that their concentration are 0.0002 M are added by 500 mL of Na2SO4 0.00002 M, determine which is the salt that precipited?

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Solubility and the common ion effect
As in systems involving dissociation of weak electrolytes, the common ion effect is of importance in solubility equilibria. Le Chatelier’s principle prdicts a decrease in solubility of saturated substance if either a soluble common ion is added. To review the effect of adding substance into the equilibrium systems, answer the following questions! No 1 Questions Given that the equilibrium in saturated solution: Ag2SO4(s) ↔ 2Ag+(ag) + SO42-(aq) Where will the eqilibrium system shift? If : a. added by SO42- ion b. added by Ag+ ion Determine the amount of Ag+ and SO42- if the equilibrium shifts to reactant! Answer ........................................................ ........................................................

2

........................................................ ........................................................

Individual assignments
What will happen if AgCl is dissolved in NaCl solution or AgNO3 solution? Compare the solubility of AgCl in NaCl solution or AgNO3 solution with solubility of AgCl in water? Change or not? No Questions answer 1 If AgCl is dissolved in NaCl x M AgCl(s) ↔ ......(ag) + .....(aq) so it will happen two ionizations. NaCl(aq)→ ......(aq) + ......(aq) Write the equation of the both ionizations! 2 Which is the ion of the product NaCl ionization that influences the equilibrium of AgCl? Where will the equilibrium shift? Based on the direction of shifting no 2, What is the effect to the solubility of AgCl? Compare with the solubility of AgCl in water! ........................................................ ........................................................ ........................................................ ........................................................

3

Conclusion

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Example
Solution :

Given Ksp for BaSO4 = 1 x 10-10, Determine the solubility of BaSO4 in Na2SO4 0,01M. The solubility of BaSO4 in Na2SO4 0,01 M = x mol/L BaSO4(s) ↔ Ba2+ (aq) + SO42-(aq) xM ~ xM ~ x M Na2SO4(aq) → 2 Na+ (aq) + SO42-(aq) 0.01 M ~ 0.02 M ~ 0.01 M BaSO4(s) Initial : a M Solubility : x M Equilibrium : (a-x) M ↔ Ba2+ (aq) + SO42-(aq) 0M 0.01 M ~ xM ~ x M + xM (0.01 + x)M

Concentration of ions at equilibrium : [Ba2+] = x M [SO42-] = ( 0.01 + x ) M ~ 0,01 M
Note : x is very small compared to 0.01 and hence the approximation that ( 0.01 + x ) M = 0,01 M is justified.

Ksp BaSO4 = [Ba2+][SO42-] ............... = ........ ........ x = ................. so the solubility of BaSO4 in Na2SO4 0.01 M is ..............................moles.L-1

1. Given that Ksp for AgCl = 1 x 10-10, determine the solubility of AgCl in: a. water b. Na2SO4 0.1 M c. NaCl 0.01 M d. CaCl2 0.005 M e. AgNO3 0.01 M

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2. The solubility of Mg(OH)2 in water is 2 x 10-4M. Determine the solubility of Mg(OH)2 in : a. Mg(NO3)2 0.01 M b. NaOH 0.0001 M c. The solution that has pH = 10

3. The solubility of AgX in AgNO3 0.001 M is 4 x 10-5M. Determine : a. Ksp for AgX b. The solubility of AgX in water

Intellectuals solve problems; geniuses prevent them (Albert Einstein)

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