1

Chemistry CHM 1310D Test 2 November 24, 2011 Darrin Richeson There were 3 versions to the exam and they appear sequentially on the following pages.

1. A 2.85 g sample of a base symbolized by B, with a molar mass of 45.09 g/mol, was dissolved in water to produce 100.0 ml of solution with a pH = 11.53. Write the equation for the reaction of B in water and calculate the ionization constant (Kb) for this base. What is the equilibrium constant for the following reaction?
BH+ +H2O B + H3O+

Answer: B + H2O BH + OH
+ -

2.85g/45.09g/mol = 6.321 x 10-2; 0.632M pH = 11.53 pOH = 14-11.53 = -log [OH ] = 2.47 [OH ] = 3.388 x 10
-3

B + H2O I C E
-3 2

BH+ +

OH-

0.632 -3.388 x 10 0.6286

-3

3.388 x 10

-3

3.388 x 10

-3

3.388 x 10
-5

3.388 x 10

-3

(3.388 x 10 ) /(0.6286) = Kb = 1.826 x 10

The reaction corresponds to Ka of the conjugate acid of base B. Calculated from the relationship Kw = Ka x Kb for a conjugate pair. Thus Ka = 10 /1.826 x 10 = 5.47 x 10
-14 -5 -10

You are given a 0.500L of a 0.660M solution of HOBr (Ka= 2.00x10-9) (a) What is the pH of this solution?
2.

Answer: HOBr 0.660 0.660-x

H+ x

OBrx

x2/0.660-x = 2.00x 10-9 Since 0.66>>2x10-9 we will use the assumption and 0.66-x = 0.66 x2 = 2.00x10-9 x 0.660 = 1.32x10-9 x = 3.63 x 10-5 This is the [H+] so pH = 4.44

(b)

You now add 18.51g of KOH to this solution. What is the pH of this solution?

Answer: Moles of HOBr = 0.500L x 0.660M = 0.330 moles HOBr 18.5 g x (1 mole/56.11g) = 0.3297 = 0.330 moles Added 0.330 moles of KOH The reaction is 1:1 KOH + HOBr K+ + H2O + OBrThis solution now contains 0.330 mole/0.5L or 0.660M OBrThis species is a base OBr- + H2O HOBr +OH- and Kb = Kw/Ka = 10-14/2.00x10-9 = 0.500 x 10-5 OBr- + H2O 0.660 0.660-x HOBr + x OHx

x2/(0.660-x) = 5.00x10-6 Since 0.660>>5x10-6 we will use the assumption and 0.66-x = 0.66 x2 = 0.660 x 5x10-6 x = [OH-] = 1.82 x 10-6 pOH = 2.74 and pH = 11.26

3. You are given a weak acid with the formula HAn (122.1g/mol). When you make a solution of 0.500 g of HAn and 0.646 g Ca(An)2 in 0.500 L of water the pH is 5.92. (a) Calculate Ka for the acid. (b) If 2.0 mL of 1.0 M HCl are added to this solution what will be the pH? (c) How many grams of NaOH should be added to this solution to get a pH of 6.25.

Answer: (a) This is a mixture of a weak acid and its conjugate base Ka = [An-][H+]/[HAn] [HAn]= 0.500 x 1mol/122.1g in 0.500L = 4.095 x 10-3 moles/0.500L [An-] = 0.646 x 1mol/282.1gx 2moles [An-]/mole of Ca salt in 0,500L = 4.58 x 10-3 moles/0.500L + [H ] = 10-5.92= 1.202 x 10-6 moles/L And Ka = 1.34 x 10-6 = 4.58x 10-3x 1.202x10-6 /4.095x10-3 Could use the equation pH = pKa +log [A ]/[HA] and will get the same number. (b) have added 2.0 x10-3 L x 1mole/L = 2.0 x 10-3 moles HCl. This reacts with An- to yield HAn. Convert 2.0 x 10-3 moles of An- to HAn. New concentrations are (4.095x 10-3 + 2.0 x 10-3)moles HAn/0.502L = 6.095x 10-3moles/0.502L (4.58x 10-3 2.0 x 10-3)moles An-/0.502L = 2.58 x 10-3moles/0.502L [H+] = Ka [HAn]/[An-] = 3.166 x 10-6 pH = 5.50 (c) For a pH =6.25, [H+] = 5.62 x 10-7M the ratio[HAn]/[An-] = [H+]/Ka = 0.4197 = (4.095 x 10-3-x)/4.58 x 10-3 + x) need to add enough OH- to adjust this ratio. x moles of OH- makes x moles of An- from x moles HAn. Solve for x: 1.922 x 10-3 + 0.4197 x = 4.095x 10-3 x 1.4197 x = 2.173x 10-3 x = 1.531 x 10-3 moles need 1.531 x 10-3 moles x 40g NaOH/mole = 0.0612 g

4 4. (a) What is the minimum value of n for the following l values? l=2 minimum n = 3 l=3 minimum n = 4

(b) Circle (neatly!) the best single answer to the following question. An atomic wavefunction represents: i. the exact location of the electron ii. the repulsion of all the electrons among themselves iii. the region of high probability for an electron around the nucleus of an atom iv. the region of high electron density for a covalent bond v. an orbit that an electron follows around the nucleus of an atom

(c) How many orbitals are available with the following sets of quantum numbers? n = 4, l = 2, ml = 1 There is only one orbital (2 electrons) n = 3, l = 3, ml = -1, ms= -1/2 zero orbitals, for n = 3 l cannot equal 3 n = 4, l = 3 ml =-3, -2, -1, 0, 1, 2, 3. There are 7 orbitals (they can hold 14 electrons)

5 5. For the reaction A C, you are told that increasing the [A] by a factor of three leads to an increase in the reaction rate by a factor of 3. You are also given the following data. [A] M 0.400 0.250 time (min) 0 15.0

Propose a form for the rate law? What is the value of the rate constant, k? What is the half-life of the reaction? How long will it take for of the original concentration of A to be consumed? Answer: The tripling of the reaction rate with triple concentration indicate that the rate law is first order in A Rate of reaction = k[A] Using the integrated rate law provided: ln[A]t ln[A]0 = -kt = -k(15min) = ln 0.250 ln 0.400 = -0.700 k = 0.0313 min-1 The half-life, t1/2 is the time when half of the original [A] has been consumed. Either use ln[A]t ln[A]0 = -kt = -0.0313 min -1(t1/2) = ln 0.200 ln 0.400 = -0.693 (t1/2) = -0.693/-0.0313 min -1 = 22.1 min or t1/2 = ln2/k = 0.693/0.0313 (these are the same!)
Can either use the integrated rate law or realize that is 2 x t1/2

ln[A]t ln[A]0 = -kt = -0.0313 min -1(t) = ln 0.1 ln 0.400 = -1.386 44.3 min.

6 5. A 2.65 g sample of a base symbolized by B, with a molar mass of 45.09 g/mol, was dissolved in water to produce 100.0 ml of solution with a pH = 11.53. Write the equation for the reaction of B in water and calculate the ionization constant (Kb) for this base. What is the equilibrium constant for the following reaction?
BH+ +H2O B + H3O+

Answer: B + H2O BH + OH
+ -

2.65g/45.09g/mol = 5.877 x 10-2; 0.5877M pH = 11.53 pOH = 14-11.53 = -log [OH ] = 2.47 [OH ] = 3.388 x 10
-3

B + H2O I C E
-3 2

BH+ +

OH-

0.5877 -3.388 x 10 0.5843

-3

3.388 x 10

-3

3.388 x 10

-3

3.388 x 10

3.388 x 10

-3

(3.388 x 10 ) /(0.5843) = Kb = 1.97 x 10-5

The reaction corresponds to Ka of the conjugate acid of base B. Calculated from the relationship Kw = Ka x Kb for a conjugate pair. Thus Ka = 10 /1.97 x 10-5 =5.08x 10-10
-14

7 You are given a 0.500L of a 0.660M solution of HOBr (Ka= 1.90x10-9) (c) What is the pH of this solution?
6.

Answer: HOBr 0.660 0.660-x

H+ x

OBrx

x2/0.660-x = 1.90x 10-9 Since 0.66>>1.90x10-9 we will use the assumption and 0.66-x = 0.66 x2 = 1.90x10-9 x 0.660 = 1.24x10-9 x = 3.54 x 10-5 This is the [H+] so pH = 4.45

(d)

You now add 18.51g of KOH to this solution. What is the pH of this solution?

Answer: Moles of HOBr = 0.500L x 0.660M = 0.330 moles HOBr 18.5 g x (1 mole/56.11g) = 0.3297 = 0.330 moles Added 0.330 moles of KOH The reaction is 1:1 KOH + HOBr K+ + H2O + OBrThis solution now contains 0.330 mole/0.5L or 0.660M OBrThis species is a base OBr- + H2O HOBr +OH- and Kb = Kw/Ka = 10-14/1.90x10-9 = 5.26 x 10-6 OBr- + H2O 0.660 0.660-x HOBr + x OHx

x2/(0.660-x) = 5.26x10-6 Since 0.660>>5.26x10-6 we will use the assumption and 0.66-x = 0.66 x2 = 0.660 x 5.26x10-6 x = [OH-] = 1.86x 10-3 pOH = 2.72 and pH = 11.27

8 7. You are given a weak acid with the formula HAn (122.1g/mol). When you make a solution of 0.500 g of HAn and 0.646 g Ca(An)2 in 0.500 L of water the pH is 5.92. (a) Calculate Ka for the acid. (b) If 2.0 mL of 1.0 M HCl are added to this solution what will be the pH? (c) How many grams of NaOH should be added to this solution to get a pH of 6.25.

Answer: (a) This is a mixture of a weak acid and its conjugate base Ka = [An-][H+]/[HAn] [HAn]= 0.500 x 1mol/122.1g in 0.500L = 4.095 x 10-3 moles/0.500L [An-] = 0.646 x 1mol/282.1gx 2moles [An-]/mole of Ca salt in 0,500L = 4.58 x 10-3 moles/0.500L [H+] = 10-5.92= 1.202 x 10-6 moles/L And Ka = 1.34 x 10-6 = 4.58x 10-3x 1.202x10-6 /4.095x10-3 Could use the equation pH = pKa +log [A ]/[HA] and will get the same number. (b) have added 2.0 x10-3 L x 1mole/L = 2.0 x 10-3 moles HCl. This reacts with An- to yield HAn. Convert 2.0 x 10-3 moles of An- to HAn. New concentrations are (4.095x 10-3 + 2.0 x 10-3)moles HAn/0.502L = 6.095x 10-3moles/0.502L (4.58x 10-3 2.0 x 10-3)moles An-/0.502L = 2.58 x 10-3moles/0.502L [H+] = Ka [HAn]/[An-] = 3.166 x 10-6 pH = 5.50 (c) For a pH =6.25, [H+] = 5.62 x 10-7M the ratio[HAn]/[An-] = [H+]/Ka = 0.4197 = (4.095 x 10-3-x)/4.58 x 10-3 + x) need to add enough OH- to adjust this ratio. x moles of OH- makes x moles of An- from x moles HAn. Solve for x: 1.922 x 10-3 + 0.4197 x = 4.095x 10-3 x 1.4197 x = 2.173x 10-3 x = 1.531 x 10-3 moles need 1.531 x 10-3 moles x 40g NaOH/mole = 0.0612 g

9 8. (a) What is the minimum value of n for the following l values? l=1 minimum n = 2 l=2 minimum n = 3

(b) Circle (neatly!) the best single answer to the following question. An atomic wavefunction represents: i. the exact location of the electron ii. the repulsion of all the electrons among themselves iii. the region of high electron density for a covalent bond iv. an orbit that an electron follows around the nucleus of an atom v. the region of high probability for an electron around the nucleus of an atom

(c) How many orbitals are available with the following sets of quantum numbers? n = 4, l = 2, ml = 1 There is only one orbital (2 electrons) n = 3, l = 3, ml = -1, ms= -1/2 zero orbitals, for n = 3 l cannot equal 3 n = 4, l = 3 ml =-3, -2, -1, 0, 1, 2, 3. There are 7 orbitals (they can hold 14 electrons)

10 9. For the reaction A C, you are told that increasing the [A] by a factor of three leads to an increase in the reaction rate by a factor of 3. You are also given the following data. [A] M 0.400 0.250 time (min) 0 9.00

Propose a form for the rate law? What is the value of the rate constant, k? What is the half-life of the reaction? How long will it take for of the original concentration of A to be consumed?

Answer: The tripling of the reaction rate with triple concentration indicate that the rate law is first order in A Rate of reaction = k[A] Using the integrated rate law provided: ln[A]t ln[A]0 = -kt = -k(9min) = ln 0.250 ln 0.400 = -0.4700 k = 0.0522 min-1 The half-life, t1/2 is the time when half of the original [A] has been consumed. Either use ln[A]t ln[A]0 = -kt = -0.0522 min -1(t1/2) = ln 0.200 ln 0.400 = -0.693 (t1/2) = -0.693/-0.0313 min -1 = 13.3 min or t1/2 = ln2/k = 0.693/0.0522 (these are the same!)
Can either use the integrated rate law or realize that is 2 x t1/2

ln[A]t ln[A]0 = -kt = -0.0522 min -1(t) = ln 0.1 ln 0.400 = -1.386 26.6 min.

11 10. A 2.85 g sample of a base symbolized by B, with a molar mass of 45.09 g/mol, was dissolved in water to produce 100.0 ml of solution with a pH = 11.33. Write the equation for the reaction of B in water and calculate the ionization constant (Kb) for this base. What is the equilibrium constant for the following reaction?
BH+ +H2O B + H3O+

Answer: B + H2O BH + OH
+ -

2.85g/45.09g/mol = 6.321 x 10-2; 0.632M pH = 11.33 pOH = 14-11.33 = -log [OH ] = 2.67 [OH ] = 2.138 x 10
-3

B + H2O I C E
-3 2

BH+ +

OH-

0.632 -2.138 x 10 0.6299

-3

2.138 x 10

-3

2.138 x 10

-3

2.138 x 10
-6

2.138 x 10

-3

(2.138 x 10 ) /(0.6299) = Kb = 7.257 x 10

The reaction corresponds to Ka of the conjugate acid of base B. Calculated from the relationship Kw = Ka x Kb for a conjugate pair. Thus Ka = 10 /7.257 x 10 = 1.378 x 10
-14 -6 -9

12 a 0.500L of a 0.660M solution of HOBr (Ka= 2.10x10-9) (e) What is the pH of this solution?
11. You are given

Answer: HOBr 0.660 0.660-x

H+ x

OBrx

x2/0.660-x = 2.10x 10-9 Since 0.66>>2.1x10-9 we will use the assumption and 0.66-x = 0.66 x2 = 2.10x10-9 x 0.660 = 1.39x10-9 x = 3.72 x 10-5 This is the [H+] so pH = 4.43

(f)

You now add 18.51g of KOH to this solution. What is the pH of this solution?

Answer: Moles of HOBr = 0.500L x 0.660M = 0.330 moles HOBr 18.5 g x (1 mole/56.11g) = 0.3297 = 0.330 moles Added 0.330 moles of KOH The reaction is 1:1 KOH + HOBr K+ + H2O + OBrThis solution now contains 0.330 mole/0.5L or 0.660M OBrThis species is a base OBr- + H2O HOBr +OH- and Kb = Kw/Ka = 10-14/2.10x10-9 = 0.476 x 10-5 OBr- + H2O 0.660 0.660-x HOBr + x OHx

x2/(0.660-x) = 4.76x10-6 Since 0.660>>4.76x10-6 we will use the assumption and 0.66-x = 0.66 x2 = 0.660 x 4.76x10-6 x = [OH-] = 1.77 x 10-3 pOH = 2.75 and pH = 11.25

13 12. You are given a weak acid with the formula HAn (122.1g/mol). When you make a solution of 0.500 g of HAn and 0.646 g Ca(An)2 in 0.500 L of water the pH is 5.92. (a) Calculate Ka for the acid. (b) If 2.0 mL of 1.0 M HCl are added to this solution what will be the pH? (c) How many grams of NaOH should be added to this solution to get a pH of 6.25.

Answer: (a) This is a mixture of a weak acid and its conjugate base Ka = [An-][H+]/[HAn] [HAn]= 0.500 x 1mol/122.1g in 0.500L = 4.095 x 10-3 moles/0.500L [An-] = 0.646 x 1mol/282.1gx 2moles [An-]/mole of Ca salt in 0,500L = 4.58 x 10-3 moles/0.500L [H+] = 10-5.92= 1.202 x 10-6 moles/L And Ka = 1.34 x 10-6 = 4.58x 10-3x 1.202x10-6 /4.095x10-3 Could use the equation pH = pKa +log [A ]/[HA] and will get the same number. (b) have added 2.0 x10-3 L x 1mole/L = 2.0 x 10-3 moles HCl. This reacts with An- to yield HAn. Convert 2.0 x 10-3 moles of An- to HAn. New concentrations are (4.095x 10-3 + 2.0 x 10-3)moles HAn/0.502L = 6.095x 10-3moles/0.502L (4.58x 10-3 2.0 x 10-3)moles An-/0.502L = 2.58 x 10-3moles/0.502L [H+] = Ka [HAn]/[An-] = 3.166 x 10-6 pH = 5.50 (c) For a pH =6.25, [H+] = 5.62 x 10-7M the ratio[HAn]/[An-] = [H+]/Ka = 0.4197 = (4.095 x 10-3-x)/4.58 x 10-3 + x) need to add enough OH- to adjust this ratio. x moles of OH- makes x moles of An- from x moles HAn. Solve for x: 1.922 x 10-3 + 0.4197 x = 4.095x 10-3 x 1.4197 x = 2.173x 10-3 x = 1.531 x 10-3 moles need 1.531 x 10-3 moles x 40g NaOH/mole = 0.0612 g

14 13. (a) What is the minimum value of n for the following l values? l=3 minimum n = 4 l=2 minimum n = 3 (b) Circle (neatly!) the best single answer to the following question. An atomic wavefunction represents: i. the region of high probability for an electron around the nucleus of an atom ii. the exact location of the electron iii. the repulsion of all the electrons among themselves iv. the region of high electron density for a covalent bond v. an orbit that an electron follows around the nucleus of an atom

(c) How many orbitals are available with the following sets of quantum numbers? n = 4, l = 2, ml = 1 There is only one orbital (2 electrons) n = 3, l = 3, ml = -1, ms= -1/2 zero orbitals, for n = 3 l cannot equal 3 n = 4, l = 3 ml =-3, -2, -1, 0, 1, 2, 3. There are 7 orbitals (they can hold 14 electrons)

15

14.

For the reaction A C, you are told that increasing the [A] by a factor of three leads to an increase in the reaction rate by a factor of 3. You are also given the following data. time (min) 0 17.0

[A] M 0.400 0.250

Propose a form for the rate law? What is the value of the rate constant, k? What is the half-life of the reaction? How long will it take for of the original concentration of A to be consumed?

Answer: The tripling of the reaction rate with triple concentration indicate that the rate law is first order in A Rate of reaction = k[A] Using the integrated rate law provided: ln[A]t ln[A]0 = -kt = -k(15min) = ln 0.250 ln 0.400 = -0.4700 k = 0.0276 min-1 The half-life, t1/2 is the time when half of the original [A] has been consumed. Either use ln[A]t ln[A]0 = -kt = -0.0276 min -1(t1/2) = ln 0.200 ln 0.400 = -0.693 (t1/2) = -0.693/-0.0276 min -1 = 25.1 min or t1/2 = ln2/k = 0.693/0.0276 (these are the same!)
Can either use the integrated rate law or realize that is 2 x t1/2

ln[A]t ln[A]0 = -kt = -0.0276 min -1(t) = ln 0.1 ln 0.400 = -1.386 50.2 min.