Chem201, Winter 2006 Name Answer key______________

Midterm N1
01/26/06
SID___________________________



1. A solution is prepared by dissolving 25.8 grams on magnesium chloride (MgCl
2
) in
water to produce 250.0 mL of solution. Molecular weight of the MgCl
2
is 95.3 g/mol.
Molecular weights of Mg and Cl are 24.3 g/mol and 35.5 g/mol, respectively.

a. Calculate the molarity of the chloride ion in the solution. (3points)

n
Cl-
= 2 n
MgCl2
= 2 (m
MgCl2
/ MW
MgCl2
) = 0.541 moles

M
Cl-
= n
Cl-
/ Volume = 0.541 moles / 0.25 L = 2.17 M


b. What is the concentration of the Cl
-
in ppm? (3points)

Cl
-
ppm = mass Cl
-
(mg) / volume = n
Cl-
MW
Cl-
/ volume = 0.541 x 35.5 x 1000 /
0.25L =

76840 ppm = 7.68 x 10
4
ppm

c. Calculate the pCl
-
value for this solution. (3points)

pCl
-
= -log [2.17] = -0.34

2. A bottle of a concentrated aqueous sulfuric acid is, labeled 98.0 wt % H
2
SO
4

(Molecular weight is 98.09 g/mol) has a concentration of 18.0 M.

a. How many milliliters of reagent should be diluted to 1.000 L to give 1.00 M
H
2
SO
4
? (5 points)

V
con
= V
dil
x (M
dil
/ M
con
) = 1000 mL x ( 1.00 M / 18.0 M) = 55.6 M

b. Calculate the density of 98.0 wt % H
2
SO
4
(5 points)

Mass of the 1 liter of H
2
SO
4
: (18 moles) (98.09) = 1.77 x 10
3
gr.
Mass of the 1 mL of H
2
SO
4
: 1.77 g

d = mass / weight % = 1.77 g / (0.98 g H
2
SO
4
/g solution) = 1.8 g/mL

3. How many milliliters of 3.00 M sulfuric acid are required to react with 4.35 g of solid
containing 23.2 g wt % Ba(NO
3
)
2
if the reaction is:

Ba
2+
+ SO
4
2-
BaSO
4
? (5 points)

Molecular weights of BaSO
4
is 233.0 g/mole and Ba(NO
3
)
2
is 261.3 g/mol.

Mass Ba(NO
3
)
2
is 0.232 x 4.35 = 1.01 g

moles Ba
2+
=
mass Ba(NO
3
)
2
MW Ba(NO
3
)
2
=
1.01g
261.34g/ mol
= 3.86! 10
"3
moles


moles H
2
SO
4
= moles Ba
2+
= 3.86! 10
"3
moles


volume H
2
SO
4
=
moles H
2
SO
4
M H
2
SO
4
=
3.86! 10
"3
moles
3 moles/ L
=1.29! 10
"3
L =1.29 mL

4. A sample is certified to contain 94.6 ppm of a contaminant. Your analysis gives
values of 98.6, 98.4, 97.2, 94.6 and 96.2 ppm. Do you results differ from the
expected result at following confidence levels: i) 95%, ii) 99% and iii) 99.9%.
(9points)


x = 97.0
s = 1.65 =

(x
i
! x)
2
"
n !1



t
calc
=
| ! x |
s
n =
| 94.6 !97.0 |
1.65
5 = 3.25



t
table
95%
= 2.776 < 3.25 Significant difference



t
table
99%
= 4.604 > 3.25 No significant difference



t
table
99.9%
= 8.610 > 3.25 No, significant difference


5. Using the appropriate statistical test, decide whether the value 216 should be rejected
from the set of result: 192, 216, 202, 195 and 204? (3 points)

Gap = 12
Range = 24


Q
calc
=
Gap
Range
=
12
24
= 0.5 < Q
table
= 0.64

Value to be retained.







6. The following data was collected when performing a spectrophotometric analysis for
cobalt.
x y
Analysis No mg Co / liter Absorbance
4 5.23 0.095
5 10.52 0.198
6 15.41 0.295
a. Using the least squares method of linear regression, generate the equation to define
the line for the absorbance vs. concentration. (10 points).

x
i
=
!
5.23+10.52 +15.41= 31.16

y
i
=
!
0.095 + 0.198 + 0.295 = 0.588

x
i
2
=
!
(5.23)
2
+ (10.52)
2
+ (15.41)
2
= 375.49

x
i
y
i
=
!
(5.23" 0.095) + (10.52" 0.198) + (15.41" 0.295) = 7.13

n = 3

D=
x
i
2
x
i
x
i
n
=
375.49 31.16
31.16 3
=155.52

m =
x
i
y
i
x
i
y
i
n
D=
7.13 31.16
0.588 3
155.52 = 0.0197

b =
x
i
2
x
i
y
i
x
i
y
i
D=
375.49 7.13
31.16 0.588
155.52 = !0.0089
Thus, linear regression line is:

y = 0.0197x !0.0089
b. Based on the equation you have generated, calculate the concentration of the Co in
the sample if the absorbance is:
i) 0.155 (2 points)

x =
0.155 !(!0.0089)
0.0197
= 8.32 mg/ L
ii) 0.265 (2 points)

x =
0.265 !(!0.0089)
0.0197
=13.90 mg/ L
7. Chloroform is an internal standard in the determination of the pesticide DDT in a
polarographic analysis. A mixture containing 0.500 mM chloroform and 0.800 mM
DDT gave signals of 15.3 A for chloroform and 10.1 A for DDT. An unknown
solution (10.0 mL) containing DDT was placed in a 100.0 mL volumetric flask and
10.2 L of chloroform (FW 119.39 g/mol, density = 1.484 g/mL) were added. After
diluting to the mark with solvent, polarographic signals of 29.4 and 8.7 A were
observed for the chloroform and DDT, respectively. Find the concentration of DDT
in unknown. (10 points)
Chloroform is S, and DDT is X:

A
x
X
= F
A
s
S
!
10.1A
0.800 mM
= F
15.3 A
0.500 mM
!F = 0.412
Concentration of the chloroform in unknown:


(10.2! 10
"6
L) (1484 g/ L) /119.39 g/ mol
0.100 L
= 0.00126 M =1.26 mM
For the unknown mixture:

A
x
X
= F
A
s
S
!
8.7 A
X
= 0.412
29.4 A
1.268 mM
! X = 0.909 mM
DDT in unknown:


0.909 mM!
100 mL
10 mL
= 9.09 mM

8. A beaker contains 250.0 mL of 0.150 molar silver ion (Ag
+
). To this beaker is added
250.0 mL of 0.300 molar bromide ion (Br
-
). What is the concentration of Ag
+
in the
final solution? K
sp
for the AgBr is 5.0 ! 10
-13
? (5 points)

AgBr ! Ag
+
+ Br
"

Final concentration of the Ag
+
and Br
-
:


[Ag
+
] = 0.150 M
250.0
250.0 + 250.0
= 0.075 M


[Br
!
] = 0.300 M
250.0
250.0 + 250.0
= 0.150 M
Br
-
ion is in excess: 0.150 0.075 = 0.075 M. [Ag
+
] = x and [Br
-
] = (x+0.075)


K
sp
= (x)(x + 0.075) = 5.0! 10
"13

Assuming x << 0.075, we have


K
sp
= (x) (0.075) = 5.0! 10
"13

x = [Ag
+
] = 6.67 ! 10
-12
.

9. Iron in the +2 oxidation state reacts with potassium dichromate to produce Fe
3+
and
Cr
3+
according to the equation:

6 Fe
2+
+ Cr
2
O
7
2-
+ 14 H
+
6 Fe
3+
+ 2 Cr
3+
+ 7 H
2
O
How many milliliters of 0.1658 molar K
2
Cr
2
O
7
are required to titrate 200.0 mL of
0.2500 molar Fe
2+
solution? (5 points)

n
Fe
2+
= 6! n
Cr
2
O
7
2"
# M
Fe
2+
V
Fe
2+
= 6M
Cr
2
O
7
2"
V
Cr
2
O
7
2"

Therefore,

V
Cr
2
O
7
2!
=
M
Fe
2+
" V
Fe
2+
6" M
Cr
2
O
7
2!
=
0.2500 M" 200.0 mL
6" 0.1658 M
= 50.26 mL
10. A mixture having a volume of 10.0 mL and containing 0.100 M Ag
+
and 0.100 M
Hg
2
2+
was titrated with 0.100 M KCN to precipitate Hg
2
(CN)
2
(K
sp
= 5!10
-40
) and
AgCN (K
sp
= 2.2!10
-16
). Calculate the concentration of the CN
-
at each of the
following volumes of added KCN:

Hg
2
2+
+ 2CN
!
"Hg
2
(CN)
2



Ag
+
+ CN
!
" AgCN
Hg
2
2+
will precipitate first and the equivalence point is at 20.00 mL. And the second
equivalence point is at 30 mL. At 5 and 15 mL there is an excess of unreacted Hg
2
2+
.
a. 5.00 mL (5points)

[Hg
2
2+
] =
20 !5
20
"
#
$
%
&
' 0.100 ( )
10
10 + 5
"
#
$
%
&
' = 0.050 M

[CN
!
] =
K
sp
[Hg
2
2+
]
=
5" 10
!40
0.050
=1.0" 10
!19
M



b. 15.00 mL (5points)

[Hg
2
2+
] =
20 !15
20
"
#
$
%
&
' 0.100 ( )
10
10 +15
"
#
$
%
&
' = 0.010 M

[CN
!
] =
K
sp
[Hg
2
2+
]
=
5" 10
!40
0.010
= 2.23" 10
!19
M

c. 35.00 mL (5points)
At 35.00 mL, there are 5 mL excess of the [CN
-
]:

[CN
!
] =
5.00
10.00 + 35.00
"
#
$
%
&
' 0.100 ( ) = 0.011 M

11. Calculate the concentration of Ag
+
in saturated solutions of Ag
2
CO
3

(K
sp
= 8.1!10
-12
) in:

! + ! + ! +
= = =
! +
2
3
2
3
2
3
2 3 2 2 2
3
2 2
] [ ] [
CO Ag CO Ag CO Ag
sp
x x x CO Ag K " " " " " "
x x


x = [Ag
+
] =
K
sp
!
Ag
+
2
!
CO
3
2"
3


Corresponding activity coefficients are taken from table (see supplemental information).


(a) 0.001 M KNO
3
(5points)


=
1
2
c
i
z
!
i
2
=
1
2
(0.001" 1
2
) + (0.001" 1
2
)
( )
= 0.001



[Ag
+
] =
K
sp
!
Ag
+
2
!
CO
3
2"
3
=
8.1#10
-12
(0.964)
2
(0.867)
3
= 0.216 mM





(b) 0.01 M KNO
3
(5points)


=
1
2
c
i
z
!
i
2
=
1
2
(0.01" 1
2
) + (0.01" 1
2
)
( )
= 0.01



[Ag
+
] =
K
sp
!
Ag
+
2
!
CO
3
2"
3
=
8.1#10
-12
(0.898)
2
(0.665)
3
= 0.247 mM



(c) 0.1 M KNO
3
(5points)


=
1
2
c
i
z
!
i
2
=
1
2
(0.1" 1
2
) + (0.1" 1
2
)
( )
= 0.1



[Ag
+
] =
K
sp
!
Ag
+
2
!
CO
3
2"
3
=
8.1#10
-12
(0.75)
2
(0.37)
3
= 0.339 mM





























Supplemental information