SOLUTIONS

“A” students work

(without solutions manual) solvent
~10 problems/night.
solute

Dr. Alanah Fitch

Flanner Hall 402
508-3119
afitch@luc.edu

Office Hours Th & F 2-3:30 pm

Define some measurement scales and units G3: Science Is referential

Module #13 molessolute
1. Molarity M=
Solution Properties Lsolution
2. mole fraction nA
Defining types of concentrations ≡ χA
For mixtures n A + nB .
molessolute
3. molality molality = m =
kg solvent

Method for Conversion from Molarity to molality Example Density of an aqueous solution of ammonium sulfate is 1.06g/mL and the

1. Assume 1 L volume
molarity is 0.886. What is the molality? NH SO ( )
4 2 4

2. Calculate moles of solute 1. Assume 1 L volume Atoms amu total

⎛ molessolute ⎞ 2. Calculate moles of solute 2N 14.01 28.02
⎜ ⎟ (1L) = molessolute ⎛ molessolute ⎞
8( H ) 8(1008
. )
⎝ Lsolution ⎠ ⎜ ⎟ (1L) = molessolute = 0.886 8.064
⎝ Lsolution ⎠ S 32.07 32.07
4( O) 4(16.00) 64
3. Calculate g of solution from d, V 3. Calculate g of solution from d, V total 133.098
⎛ 10 3 mL ⎞
d solution ⎜ ⎟ (1Lsolution ) = g solution ⎛
⎜ 106
.
g ⎞ ⎛ 1000mL ⎞
⎟⎜ ⎟ (L ) = 1060g solution
⎝ L ⎠ ⎝ mL ⎠ ⎝ L ⎠ solution
4. Calculate g of solute from M
⎛ g ⎞ 4. Calculate g of solute from M
M (1Lsolution )⎜ solute ⎟ = g solute ⎛ mol ⎞ ⎛ 133.098 g solute ⎞
⎝ molsolute ⎠ ⎜ 0.886 ⎟ (1Lsolution )⎜ ⎟ = 117.9248 g solute
⎝ L ⎠ ⎝ molsolute ⎠
5. Subtract to get g of solvent
5. Subtract to get g of solvent
g solution − g solute = g solvent
1060 g solution − 117.9248 g solute = 942.1g soluent
6. Calculate g solute/g solvent
molessolute 6. Calculate g solute/g solvent
molality = m = molality = m =
molessolute 0.886molessolute
= = 0.941
kgsolvent kg solvent 0.9421kg solvent

1
 Method for Conversion from molality to Molarity Example Density of an aqueous solution of KOH is 1.43g/mL and the molality is
1. Assume 1 kg solvent 14.2. What is the molarity?
2. Calculate moles of solute 1. Assume 1 kg solvent
⎛ molessolute ⎞ 2. Calculate moles of solute
⎜ ⎟ 1kg solvent = molessolute
⎝ kg solvent ⎠ ⎡ 14.2molesKOH ⎤
⎢ 1kgwater ⎥ [1kgwater ] = 14.2molesKOH
3. Calculate g of solute from MM ⎣ ⎦
⎛ ⎞
(moles )⎜⎝ moles
g solute
⎟ = g solute 3. Calculate g of solute from MM
solute
solute ⎠
⎛ 39.10 + 16.00 + 108
. gKOH ⎞
4. Sum masses to get total mass of solution
[14.2molesKOH ]⎜ ⎟ = 797.756 gKOH
⎝ moleKOH ⎠
1000g solvent + g solute = g solution 4. Sum masses to get total mass of solution

5. Calculate V of solution from density g solution = g H2 O + g KOH = 1000 g + 797.756 g = 1797.756 g solution
⎛ solution ⎞ ⎛ L ⎞ 5. Calculate V of solution from density
( g solution )⎜⎝ mL ⎟⎜ ⎟ = ( Lsolution )
g solution ⎠ ⎝ 10 3 mL ⎠
⎛ 1mLKOHsolution ⎞
6. Calculate moles/V (1797.756g )⎜⎝ 143 ⎟ = 1,257.17mL
KOHsolution ⎠
. g
solution

⎛ molessolute ⎞
M=⎜ ⎟ 6. Calculate moles/V
⎝ Lsolution ⎠ 14.2 moles , KOH
moles
M= = = 11296
.
Lsolution 1257
. LKOHsolution

Methods of measurement are related but not equivalent

“A” students work
16
Density
50 (without solutions manual)
14
Molality 45 ~10 problems/night.
Weight %
40
12
Molaity or (densityx10)

35
Dr. Alanah Fitch
weight percent

10
30 Flanner Hall 402
8 25 508-3119
afitch@luc.edu
20
6
Office Hours Th & F 2-3:30 pm
15
4
10
2 Module #13
5
Solution Properties
0 0
0 2 4 6 8 10 12 14 16
Molarity
Water/Salt Solutions 1

2
 SOLUTIONS A mixture is usually plotted as variation in mole fractions
nA nB nB + nB
χ A + χB = + = =1
nB n A + nB . n A + nB . n A + nB .
Any two components A and B ≡ χB
Mixed in any mole fraction n A + nB . nA
≡ χA
n A + nB .
1

0.8

mole fraction
0.6

0.4

0.2

0
0 0.2 0.4 0.6 0.8 1
B A
moles of A
Pure B Pure A
Solvent is usually Solute is usually
Considered the “dissolver” Considered the “dissolved”

mixture

Solvation Diagrammed as an Example of Hess’s Law

SOLUTIONS MgSO4 ,s ⎯⎯⎯ 2+
⎯→ Mg aq
H O
2
+ SO42,−aq ∆ H = − 912
.
kJ
mol
solvent
Any two components A and B
Mixed in any mole fraction
solute

-1284.9kJ
mole

-1376.1kJ
mole

water
2+ kJ
MgSO4 ,s ⎯⎯⎯ ⎯→ Mg aq + SO42,−aq ∆ H = − 912
H O
2
.
mol

3
NH 4 NO3( s ) → NH 4+( aq ) + NO3−( aq ) ∆ H = + 281
. kJ NH 4 NO3( s ) ⎯⎯⎯⎯→ NH 4+( aq ) + NO3−( aq )
water
∆ H = + 281
. kJ
http://www.qtp.ufl.edu/~roitberg/pdf/2002_04.pdf
http://www.lsbu.ac.uk/water/magic.html

For most salts,

NH4 NO3( s) + heat → NH4+( aq ) + NO3−( aq ) heat will increase solubility

∆ H = + 281
. kJ
Aquated
Ammonium

Aquated
nitrate

SOLUTIONS
“A” students work
(without solutions manual) solvent
~10 problems/night.

solute

Dr. Alanah Fitch

Flanner Hall 402
508-3119
afitch@luc.edu

Office Hours Th & F 2-3:30 pm

Module #13
Solution Properties
water organic
Organic/Solute MgSO4 ,s ⎯⎯⎯ 2+
⎯→ Mg aq
H O
2
+ SO42,−aq ∆ H = − 912
.
kJ
mol
Solutions

4
 Like Dissolves Like
What trends do you see here? similar intermolecular forces between
solute-solute
solvent-solvent
imply solute-solvent interaction will be decent

g solute
s=
g solvent
What trends do you see here?

Soluble in water? Soluble in water?

Context Slide Context Slide

Solute-Solvent interactions: Vitamin C and Lead

Vitamin C is more soluble in the aqueous

Phase of the body (urine) than other
Vitamins which are stored in fat. Vitamin C is water soluble
so it is excreted from the
body

the longest you can last

without serious disease
without consuming fresh
vitamin C is 6 months

Sir Franklin

5
Context Slide Context Slide

John Hartnell

Context Slide
“A” students work
(without solutions manual)
~10 problems/night.

Dr. Alanah Fitch

Flanner Hall 402
508-3119
afitch@luc.edu

Office Hours Th & F 2-3:30 pm

Module #13
Solution Properties
Gas/Solvent Solutions
Raoult’s Law, Freezing
Point, Boiling Pt changes
Osmotic Pressure

6
 All ⎯⎯⎯⎯⎯⎯→ Ag nA
rate escapes
SOLUTIONS n A + nB .
≡ χA =1
Number of escapes will depend on
1. Number of molecules with energy>>
solvent
intermolecular forces
2. Fraction of molecules with that
solute energy at some the given
temperature
3. The Surface area available for
escape
4. Escapes independent of what gas
is doing

Agg ⎯⎯⎯⎯⎯⎯→ Al
rate sticking

Number of returns will depend on

1. Intermolecular forces in gas
phase greater than collisional
Liquid Consider first case where A energy Liquid Phase
Liquid Gas Solution Is a pure substance 2. Fraction of molecules at with less In a container
energy than intermolecular
Component A forces at that temperature Prediction 1
Component B
nA 3. Sticking followed by dropping does 1. T8, more escapes, more gas phase A
≡ χA =1 2. T8, less sticking (fewer returns)
n A + nB . not depend upon the surface area

Predict: nA
1. T8 6more gas vapor Intermolecular ≡ χA =1 From earlier chapter we learned of kinetic energy:
n A + nB . Maxwell’s Distribution
2. T8 6less sticking of forces
1 2
gases more gas vapor Ek = mv
2
⎡ − ∆ Hvaporization ⎤ µ
⎢ ⎥
Ppure liquid = e ⎣
RT ⎦ 3kT σ
urms = RT
g molecule
Exponential represents fraction
of molecules at temperature T
2
αEK
with sufficient energy to break
1 ⎡ 3kT ⎤ However, only a fraction of
intermolecular forces E k = mass of molecule ⎢ ⎥ molecules at a given emperature that
()Hvaporization) 2 ⎣ mass of molecule ⎦ average speed, and therefore,
Average energy
1 ⎡ − ∆ Hvaporization ⎤ ⎛1 ⎞⎛ 3kT ⎞
⎢ ⎥ Liquid Phase E k = ⎜ mass of ⎟⎜ ⎟ If you assume a normal distribution
⎝2 molecule
⎠ ⎝ mass of molecule ⎠
Ppure liquid = e
T⎣ R ⎦
In a container for the “bell curve” you can calculate
the fraction of molecules with an
−−11 ⎛ 3kT ⎞ energy above the average value
TT↑↑;;eeTT ↑↑; PAo ↑ Ek = ⎜ ⎟
⎝ 2 ⎠ 1⎛ x− µ ⎞ 2
− ⎜ ⎟ −
E molecule
−
E mole
f ( x) = e 2⎝ σ ⎠
f ( x) = e =e
Math for the fraction of molecules with sufficient energy
kT RT
Is on next slide, if desired Review

7
 All ⎯⎯⎯⎯⎯⎯→ Ag
rate escapes
SOLUTIONS
Number of escapes will depend on
1. Number of molecules with energy>>
solvent
intermolecular forces
2. Fraction of molecules with that
energy at some the given solute
temperature
3. The Surface area available for
escape
4. Escapes independent of what gas
is doing

Agg ⎯⎯⎯⎯⎯⎯→ Al
rate sticking

Number of returns will depend on

1. Intermolecular forces in gas
phase greater than collisional
energy Liquid Phase Liquid One way to diminish
2. Fraction of molecules at with less In a container Liquid Gas Solution Surface area is to add solute to
energy than intermolecular Pure substance A
forces at that temperature Component B Component A
Prediction 2 nA
3. Sticking followed by dropping does
1. Surface Area 9, less escapes, less gas A ≡ χA <1
not depend upon the surface area
2. Surface Area 9, no impact on rate sticking n A + nB .

A mixture is usually plotted as variation in mole fractions

nA nB nB + nB
χ A + χB = + = =1
n A + nB . n A + nB . n A + nB .
nA 99 A
nA ≡ χA = 10
≡ χA n A + nB . 1B + 99 A
n A + nB .
1
Within every layer of liquid (10x10) 10
0.8
there are 99A and 1B
How has the surface Area available
for escape changed?
mole fraction

0.6

0.4 New Surface Area = χ A (Original Surface Area )

0.2 How will vapor pressure change?

nB
≡ χB
0 n A + nB . We just made a prediction!
0 0.2 0.4
moles of A
0.6 0.8 1
Al ⎯⎯⎯⎯⎯⎯→ Ag
rate escapes PA = χ A PAo
Pure A
Pure B
Predict: Raoult’s Law
1. T8 6more gas vapor
2. Surface area 9 6less gas vapor
mixture
3. Escapes independent of gas!!

8
 Boiling Point elevation
⎡ − ∆ H vaporization ⎤ ⎡⎢ TA ,bp − TA ,bp ⎤⎥
o

1 ⎡ − ∆ Hvaporization ⎤ ln(1 − χ B ) = ⎢ ⎥⎢ −
ln P pure liquid = ln P = ⎢ o
⎥ ⎣ R ( )( )
⎦ ⎣ TA,bp TAo,bp ⎥⎦
PA0 A
T⎣ R ⎦ If P small If numbers
PA 1 ⎡ − ∆ H vaporization ⎤ Similar altho
ln PAo,b = o ⎢ ⎥ Not the same
Tb , A ⎣ R ⎦ I hate drivations
⎡ o ⎤
⎡ − ∆ H vaporization ⎤ ⎢ TA,bp − TA ,bp ⎥
⎡ P ⎤ ⎡ − ∆Hvaporization ⎤ ⎡ 1 χB = ⎢ ⎥⎢ −
1⎤ ⎣ R
( )
⎦ ⎢ TAo,bp
2 ⎥
ln ⎢ 2 ⎥ = ⎢ ⎥⎢ − ⎥ ⎣ ⎦⎥
⎣ P1 ⎦ ⎣ R ⎦ ⎣ T2 T1 ⎦ ⎡ ⎤
− ∆ H vaporization ⎥ o
= ⎢
nB
∆T
nB + n A ⎢
( ) ⎥ A ,bp
Clausius-Clapyeron Equation 2
o
Pure A ⎢⎣ R TA ,bp ⎥⎦
0 ⎡ PA ,bp ⎤ ⎡ − ∆ H vaporization ⎤ ⎡ 1 1 ⎤
ln ⎢ o ⎥ = ⎢ − o ⎥ nB < < n A
⎥⎢
⎢⎣ PA ,bp ⎥⎦ ⎣ R ⎦ ⎢⎣ TA,bp TA ,bp ⎥⎦ nB
= k∆ TAo,bp
PA = χ A PAo PA
= χA =
nA
χ A = 1 − χB =
nB nA
PA0 n A + nB n A + nB nB k
Assumes effect of “B” is to simply block the surface = ∆ TAo,bp
⎛ kg A ⎞ ⎛ kg A ⎞
Raoult’s Law No interaction of “B” (solute) with “A” (solvent) ⎡ − ∆ H vaporization ⎤ ⎡ 1
ln(1 − χ B ) = ⎢
1 ⎤
− o ⎥ (n )⎜⎝ mole ⎟ ⎜ ⎟ ∆ PA = χ B PAo
⎥⎢ A
A⎠ ⎝ mole A ⎠
⎣ R ⎦ ⎢⎣ TA ,bp TA ,bp ⎥⎦
⎡ − ∆ H vaporization ⎤ ⎡⎢
ln(1 − χ B ) = ⎢ ⎥⎢
TAo,bp
−
TA,bp ⎤
⎥
molal B = k ' ∆ TAo,bp Kb molal B = ∆ TAo,bp
⎣ R ( )( ) ( )( ) ⎥⎦
⎦ ⎣ TA,bp TAo,bp TAo,bp TA,bp 1
molal B = ∆ TAo,bp
k'

Boiling Point elevation SOLUTIONS

Freezing Point depression solvent

solute
Constants for water

Kb molal B = ∆ TAo,bp Kb = 0.52

C o

molal

K f molal B = ∆ TAo,mp K f = 186

.
C o

molal
Liquid The other extreme is to
Liquid Gas Solution nA
≡ χ A <<<<< 1
Component A n A + nB .
Component B

9
 When “A” is completely surrounded by “B” When “A” is completely surrounded by “B”

Predictions
Ain B liquid ⎯⎯⎯⎯⎯⎯→ Ag
rate escapes
1. Greater PAmore collisions with B,
greater condensation, greater
1 Surface area for A solution concentration
2 Escapes of A from B when
energy is larger than A/B PA
intermolecular forces χA =
h
Math (slide after
next)
Ag ⎯⎯⎯⎯⎯⎯→ Ain B liquid
rate sticking

1. Number of possible A/B collisions

C g = k H PA
(Partial Pressure of A) (PA)
2. Intermolecular forces of A/B in
gas phase greater than collisional A/B intermolecular forces
energy
3. Fraction of molecules with Liquid Phase of B Liquid Phase of B
intermolecular energy greater than In a container 2. Greater T less collisions in whch In a container
collisional energy increases as T intermolecular forces allow
goes down. sticking, less solution
4. No dependence on surface area concentration

if n A < < n B
Henry’s Law
PA = (break A − B energy )χ A ⎛n ⎞ Molality
PA = k '' ⎜ A ⎟
⎝ mB ⎠ When
PA = kχ A mb in kg

⎛ nA ⎞ 1 ⎛n ⎞
PA = k ⎜ ⎟ PA = ⎜ A ⎟ = k H PA
⎝ n A + nB ⎠ k'' ⎝ mB ⎠

⎛n ⎞
Solubility in water
PA = k ⎜ A ⎟
⎝ nB ⎠
C g = kPA
Prediction 2: ⎛ ⎞
Henry’s Law
As temp goes up, fewer ⎜ ⎟ kH = Henry’s constant
⎛ mB ⎞ ⎜ ⎟
C g = k H PA Gas phase collisions between
A/B allow them to stick,
PA = k ' ⎜ ⎟
⎝ nB ⎠ ⎜
nA
⎛ mB ⎞ ⎟
⎜⎜ (n B )⎜ ⎟⎟ kH =
nB
⎝ n B ⎠ ⎟⎠
Less condensation
Prediction 1 ⎝ (break A − B energy )molal B
For the math hungry

10
 VP
P Context Slide PA=PAo
Henry’s Law Raoult’s Law 60

Slope is Slope is a function Reflects dioxin-water interactions

A function of Of Partial Pressure of dioxin
50
interactions Viktor Yushchenko
Henry’s Law
interactions 2004, Ukrainian
Opposition candidate
40 For president,
Pdioxin Poisoned by dioxin
Pure solvent

P (mm Hg)
Raoult’s Law
30
χA Reflects dioxin-dioxin interactions

C g = k H PA
Surface area for escape
PA = χ A PAo 20
Cl O Cl

Cl O Cl
Partial Pressure Raoult’s Law
10 Cl O Cl
Cl O Cl

Everything in between Vapor Pressure

Is hard to predict Cl O Cl
Cl O Cl
0
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
Mole Fraction Dioxin in Water
n Dioxin
≡ χ Dioxin
nwater + n Dioxin .

Same concept for

Galen, 170 Marie the Jewess, 300 Jabir ibn Galileo Galili Evangelista Torricelli Jean Picard Daniel Fahrenheit Blaise Pascal Robert Boyle, Isaac Newton Anders Celsius
Hawan, 721-815 An alchemist 1564-1642 1608-1647 1620-1682 1686-1737 1623-1662 1627-1691 1643-1727 1701-1744

As ⎯⎯⎯⎯⎯⎯→ Ag
rate escapes
10

Ag ⎯⎯⎯⎯⎯⎯→ As
rate sticking
Charles Augustin James Watt Luigi Galvani Count Alessandro G Amedeo Avogadro John Dalton William Henry Jacques Charles Georg Simon Ohm Michael Faraday B. P. Emile Germain Henri Hess
Coulomb 1735-1806 1736-1819 1737-1798 A A Volta, 1747-1827 1756-1856 1766-1844 1775-1836 1778-1850 1789-1854 1791-1867 Clapeyron
1799-1864
1802-1850
10
Sublimation

Dmitri Mendeleev Johannes D. J. Willard Gibbs

Justus von Thomas Graham Richard AC E James Joule Rudolph Clausius William Thompson Johann Balmer Francois-Marie James Maxwell 1834-1907 Van der Waals 1839-1903
Liebig (1803-1873 1805-1869 Erlenmeyer (1818-1889) 1822-1888 Lord Kelvin, 1825-1898 Raoult 1831-1879 1837-1923
1825-1909 1824-1907 1830-1901

Solid phase
In a box

Ludwig Boltzman Henri Louis Henri Bequerel Jacobus van’t Hoff Johannes Rydberg J. J. Thomson Heinrich R. Hertz, Max Planck Svante Arrehenius
Walther Nernst Marie Curie Fritz Haber Thomas M Lowry
1844-1906 LeChatlier 1852-1908 1852-1911 1854-1919 1856-1940 1857-1894 1858-1947 1859-1927 1864-1941 1867-1934 1868-1934 1874-1936
1850-1936

Gilbert N Johannes Lawrence Henderson Niels Bohr Erwin Schodinger Louis de Broglie Friedrich H. Hund Rolf Sievert, Fritz London Wolfgang Pauli Werner Karl Linus Pauling Louis Harold Gray
Lewis Bronsted 1878-1942 1885-1962 1887-1961 (1892-1987) 1896-1997 1896-1966 1900-1954 1900-1958 Heisenberg 1901-1994 1905-1965
1875-1946 1879-1947 1901-1976

Fitch Rule G3: Science is Referential

11
Imagine: Two volumes of water Osmotic pressure (pressure driving
1. is “pure” n RT
⎛
⎜⎜
nelectrolyte ⎞
⎟⎟ = 0 = χ 1 π= B = [ B] RT water from one compartment to
⎝ nwater + nelectrolytes .⎠ V another) is directly related to the
concentration of the solute, B.
2. the second has large salt mole fraction
⎛ nelectrolyte ⎞ 1. This provides a convenient way to measure molar masses.
⎜⎜ ⎟⎟ = 0.2 = χ 2
+ .
⎝ water electrolytes ⎠
n n

3. There is a barrier 2. Has huge physiological implications

between them
which
is impermeable
to the
electrolytes
Barrier (memrane)
4. Surface Only water (not
area for solute)
water Is allowed to pass
escape is 5. Escapes 1> Escapes 2
less in cube 6. Water moves 1 to 2
2 7. As water in 2 increases
Pressure builds up
against membrane

Visualization Context
Water will move from the pure solvent to the solute When not well regulated the extracellular fluid increases and
containing container. edema (bursting of cells) results

Cucumber placed in
Cucumber high salt solution Prune Prune placed in
pure water
Aka =Pickle
Aka = Plume

12
Context Water motion across cell
membranes is driven by
osmotic pressure related to the salt
concentration gradient

Typical ion concentrations in vertebrates and invertebrates

Ion Cell (M) Blood (M)
K+ 0.139 0.004
Na+ 0.012 0.145
Cl- 0.004 0.116
HCO3- 0.012 0.029
A Student who did NOT take X- 0.138 0.009
Mg2+ 0.0008 0.0015
Gen Chem Ca2+ <0.0000002 0.0018

Normal horse blood

http://images.google.com/imgres?imgurl=http://www.vetmed.auburn.edu/distance/clinpath/morphol/sa10.jpg&imgrefurl=http://www.ve
tmed.auburn.edu/distance/clinpath/morphol1/&h=80&w=120&sz=3&hl=en&start=10&tbnid=jyQ0sNBf3dS1HM:&tbnh=59&tbnw=88&pr
The equations n B RT
ev=/images%3Fq%3Dcrenation%26svnum%3D10%26hl%3Den%26client%3Dfirefox-a%26channel%3Ds%26rls%3Dorg.mozilla:en-
π= = [ B] RT
PA = PA0 χ A
US:official%26hs%3Dk0K%26sa%3DGcells
V

Raoult’s Laws
∆ PA = χ B P o
A

Bumpy Horse blood cells are dessicating K f molal B = ∆ TAo,mp

Normal horse
Red blood cells
= “crenation” Derived from
Raoult’s Law
Kb molal B = ∆ TAo,bp
Colligative Properties
Depend on Solute Conc.

Normal RBC
Hemolysis RBC
Rupture of RBC
www.healthenlightenment.com/hemolysis.jpeg
C g = kPA Henry’s Law
Depends primarily on solvent

13
 “A” students work EXAMPLE Calculations
(without solutions manual)
~10 problems/night. Example A solution contains 102 g of sugar, C12H22O11, in 375 g of water.
Calculate the vapor pressure lowering at 25 oC (vp of pure water = 23.76 mm Hg

Dr. Alanah Fitch
Flanner Hall 402
508-3119
afitch@luc.edu
Office Hours Th & F 2-3:30 pm
Module #13
Solution Properties
Example Calculations
Raoult’s Law, Henry’s Law,
Boiling Pt elevation
Freezing Pt depression
Example Calculate the concentration of CO2 in a soft drink that is bottled with
a partial pressure of CO2 of 4.0 atm over the liquid at 25oC. The Henry’s law
constant for CO2 in water at this temperature is 3.1x10-2 mol/L@atm.
Example The solubility of pure nitrogen in blood at body temperature, 37 oC,
And one atmosphere nitrogen is 6.2x10-4 M. If a diver breathes air (χN2 = 0.78) at a
depth where the total pressure is 2.5 atm, calculate the concentration of nitrogen in
his blood.
Example: You add 1.00 kg of ethylene glycol (C2H6O2) antifreeze to your car
radiator, which contains 4450 g of water. What are the boiling and freezing
points of the solution? Kb of water is 0.512 (oC/m) and Kf of water is 1.86 (oC/m).
Osmotic Pressure Example Calculation:
What is the osmotic pressure related to a 0.10 M CaCl2 solution?

Example 1 A solution contains 102 g of sugar, C12H22O11, in 375 g of water. Example 1 A solution contains 102 g of sugar, C12H22O11, in 375 g of water.
Calculate the vapor pressure lowering of water at 25 oC (vapor pressure of pure Calculate the vapor pressure lowering of water at 25 oC (vapor pressure of pure
water = 23.76 mm Hg water = 23.76 mm Hg

What do we know? χ2 P1o = ∆P [0.0141][23.76mmHg] = 0.335mmHg

sugar in water (sugar= solute; water= solvent)
molessolute Molar mass: 12C = 12x12= 144
χ solute = 22H = 22
What equations might apply? molessolvent + molessolute 11O = 11x16 = 176
Vapor pressure lowering
total = 342

∆ PA = χ B PAo ⎡ 1molsugar ⎤
[102 gsugar ⎢ ] ⎥
⎢⎣ 342.30 gsugar ⎥⎦
What information is irrelevant? (Red herring) χ sugar =
⎡ 1molwater ⎤ ⎡ 1molsugar ⎤
none. [375gwater ]⎢
⎣ 18.02 gwater ⎦
[
⎥ + 102 gsugar ⎢ ] ⎥
⎢⎣ 342.30 gsugar ⎥⎦

0.298molsugar
χ sugar = = 0.0141
20.8molwater + 0.298molsugar

14
 Example 3The solubility of pure nitrogen in blood at body temperature, 37 oC,
Example 2 Calculate the concentration of CO2 in a soft drink that is bottled and one atmosphere of nitrogen is 6.2x10-4 M. If a diver breathes air (χN2 = 0.78) at a
with a partial pressure of CO2 of 4.0 atm over the liquid at 25oC. The Henry’s depth where the total pressure is 2.5 atm, calculate the concentration of nitrogen in
law constant for CO2 in water at this temperature is 3.1x10-2 mol/L@atm. his blood.

Solute? Solute? N2
Solvent? Solvent? Blood
Equation?
Red Herrings?
Equation?
Red Herrings?
C g = k H Pg
Cg = kPg

⎛ mol ⎞ mol
. x10 − 2
Cg = ⎜ 31 ⎟ ( 4.0atm) = 0124
.
⎝ L − atm ⎠ L
Sig figs

Example 3The solubility of pure nitrogen in blood at body temperature, 37 oC,

and one atmosphere nitrogen is 6.2x10-4 M. If a diver breathes air (χ N2 = 0.78) at a Example 4: You add 1.00 kg of ethylene glycol (C2H6O2) antifreeze to your car
depth where the total pressure is 2.5 atm, calculate the concentration of nitrogen in radiator, which contains 4450 g of water. What are the boiling and freezing
his blood. points of the solution? Kb of water is 0.512 (oC/m) and Kf of water is 1.86 (oC/m).

∆Tb = kb [ molality ]
Unknown, how can we
⎡ M ⎤ ∆Tf = k f [ molality ]
Get it?
C g = ⎢ 6.2 x10 −4 ⎥ (195
. atm) = 1209
. x10 −3 M
C g = k H Pg ⎣ atm ⎦
⎛ o
C ⎞
⎟ [molality ] ⎛ C ⎞
o
∆ Tb = ⎜ 0.512
⎟ [molality ]
6.2 x10 M = k (1atm)
−3 ∆ T f = ⎜ 186
−4
C g = 12
. x10 M ⎝ molality ⎠
⎝
.
molality ⎠
[molality] =
mol solute ⎛ o
C ⎞
6.2 x10 − 4 M M kg solvent ∆ T f = ⎜ 186
⎝
. ⎟ 3.62mC2 H 6 O 2 = 6.73o C
molality ⎠
k= = 6.2 x10 − 4
(1atm) ⎛ ⎞3⎛ 1molC2 H 6 O2 ⎞
3
10 g g ⎞ ⎛ 1molC H O ⎞
(100 H O )⎜ )⎛⎜⎛10
3
atm . (100 10⎟ ⎜g⎟⎞⎜⎛ 1molC H O⎟ ⎟⎞
(100 ⎝ 1⎝)kg
2 6 2
.kgC
. kgC
2
kgC HH OO
6 2
⎜ 1kg ⎟ ⎜.07.07
⎠ ⎝ 62 gC H H
2 6 2
O ⎠ ⎟ 161
. molC H O
[molality ] 1kg ⎠⎠⎝⎝62 gC H OO=⎠⎠
2 6 2
62.07gC
[[molality
molality]]==
⎝
2 6 2 2 6 2 2 6 2
= 2
2
6 2
6 2 = 3.62m
⎛ 1⎛kg1kg ⎞ ⎞ 4.450kg
Cg = kPg 4450 2 O⎜O⎜ 3 ⎟ ⎟
gHgH
4450 kg solvent
2⎝ 10 g3⎠
⎝ 10 g ⎠
Unknown how can we get it?
Dalton’s Partial Pressure Law! ⎛ o
C ⎞
∆ Tb = ⎜ 0.512 ⎟ 3.62mC2 H 6 O 2 = 185
. oC
⎝ molality ⎠ The radiator will freeze at 32-6.73 oC

PN 2 = ( 0.78)( 2.5atm) = 195

=25.27 oC
PN 2 = X N 2 Ptotal . atm The radiator will boil at 101.85 oC

15
Osmotic Pressure Example Calculation: Context Slide: Preparation for your papers
What is the osmotic pressure related to a 0.10 M CaCl2 solution? Reference Data for Risk Assessment

n B RT
π= = [ B] RT KOW =
g solute / Loc tan ol
V Cg = kPg g solute / Lwater
⎡⎡ mol⎤⎤⎡⎡
mol LL⋅⋅atm
atm⎤⎤
ππ == [[BB]]RT
RT == 33⎢⎢010
010
.. ⎥⎥⎢⎢00.0821
.0821 [[298
298KK]] = 7.2atm
⋅⋅ KK⎥⎦⎥⎦
Your paper
⎣⎣ LL ⎦⎦⎣⎣ mol
mol for a compound of interest

Where did this come from? 3 moles solute find, listing source of data
s
2+
CaCl2 ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→ Ca aq + 2Claq−
strong electrolye complete Kow
KH
g solute
In order to control this pressure the kidney s= octanol
g H2 O H3C OH

regulates the amount of Ca2+, Na+ and other ions in the

blood
Set a reference state to compare all chemicals Why would this
Lead can cause significant Be important?
solubility in water (s)
Blood pressure problems by interfering solubility between water and octanol (Kow) Hint, think about
Kidney regulation of ions KH Vit. C and Vit A

SOLUTIONS
“A” students work
(without solutions manual) solvent
~10 problems/night.
solute

Dr. Alanah Fitch

Flanner Hall 402
508-3119
afitch@luc.edu

Office Hours Th & F 2-3:30 pm

Module #13
Solution Properties
B A
copper tin
Solid/solid solutions
As an example of importance
Of freezing point depression

16
Context Slide Bronze phase diagram Context Slide
A Different Kind of Phase Diagram as Tin is added to Copper

Liquid Liquid Phase

Temp

Solid Solid
+
Liquid
nA Solid phases
nB 100%A ≡ χA
≡ χB n A + nB .
n A + nB . 100%B
Same idea of mole fraction

Bronze phase diagram Context Slide Egyptian Glass how did they do it? Context Slide
as Tin is added to Copper
These represent 1300B.C.
Viscosity = measures flow
2. Grind up and various unit cell low viscosity = easy flow
mix tin to copper structures (face
and you can lower centered cubic, etc.) Campfire Temps
the melting point Liquid Phase adopted

1. Temperature
Range of early
“campfires”

Additives to
3. Bonus point: The quartz
final material Solid (SiO2) allow
harder than The glass to
copper!! + Melt (becomes
Liquid Less viscous)
4. Many early economics
At campfire
Of societies
Temperatures.
Collapsed as fuel
(forests) ran out
5. England’s interest in controlling Ireland
Was initially over wood supply

17
Context Context
Pb2+

Sugar of Lead =Pb(CH3COO)2

−
⎡ •
••
• ⎤
⎢ •O• H ⎥
⎢ •• ⎥
Pb2+
2 O = C − C − H⎥
⎢
⎢ •• ⎥
⎢ ⎥
⎢ H ⎥
⎣ ⎦
Where does the negative charge reside? Renal biopsy
Is this acetate anion q/r large or small? 26 year old
Is this acetate anion charge dense or not? Ship paint stripper
Will acetate “hold on” to Pb2+ or will water win?

Failure of kidneys leads to deposition of

Context Excess uric acid to joints = Gout
Context

Immersion of the body Up to head creates a

Pressure gradient in the blood volume towards the
head; Body compensates with increased urine to Initial symptoms are hallucinations
lower Blood volume to brain; Increased urination
leads to increased loss Of electrolytes (lead)
creepy bugs, etc.

Tetraethyl lead poisoning is highly acute leading very rapidly to edema

Why and what does this have to do with osmotic pressure?

18
 Pb(CH 3 CH 2 ) 4
•
Context Tetraethyl lead has what kind of structure? Context •C •
Hint: Valence Shell Electron Pair Repulsion • •
Pb(CH 3 CH 2 ) 4 model Bond strength • C − Pb − C •
• •
- is the Pb-C bond as
• •C • Floppy CH3CH2
Valence electrons of atoms •C • strong as a true fully •
5(4) 20 covalent C-C bond? chain buries Pb
single bonds 2(4) 8 • • Bond enthalpies
remainder to Cs 12 • C − Pb − C • C-C 368
• • NO!!!
Pb-C 206.7kJ/mol
VSEPR = AX4=tetrahedral •C •
• Pb(CH 3 CH 2 ) 4 → Pb(CH3 CH 2 ) 3 + CH 3 CH 2
Tetrahedral arrangement is
Pb(CH3 CH2 ) 4 → Pb(CH 3 CH 2 )
important because the lead Carbon gets +•
the electron 3 + • CH 3 CH 2
is buried beneath the organic
CH3CH2 chains - making it
lipid soluble. Floppy CH3CH2
chain buries Pb
Chloride ion gets
buried in the ( +
)
Pb CH3 CH 2 3 + Cl − → Pb CH 3 CH 2 ( ) Cl
3
carbon chain center, making it lipid soluble

Context Context

Cl Typical ion concentrations in vertebrates and invertebrates

Ion Cell (M) Blood (M)
K+ 0.139 0.004
Na+ 0.012 0.145
Cl- 0.004 0.116
HCO3- 0.012 0.029
PV= energy X- 0.138 0.009
Mg2+ 0.0008 0.0015
Triethyllead carries chloride ions across the cell membrane Ca2+ <0.0000002 0.0018
disrupting the energy cycle of the cell and the osmotic
pressures - ultimately results in cell death by “popping” (edema)

19
“A” students work
(without solutions manual)
~10 problems/night.

Alanah Fitch
Flanner Hall 402
508-3119
afitch@luc.edu

Office Hours Th & F 2-3:30 pm

Module #13
Solution Properties
END

20