1st Year Chemistry Lecture 6

Midterm
Oct. 8, 2014, 5:00 pm

Chapters 1-‐7
Room GYM GYM HW214 HW215 HW216 SW128 SW143 SW309 SW319
Front Back
Practical 1-13, 14, 29, 30 37, 49 31 - 35 19, 47, 36, 38, 39 - 41, 42 - 45
Section 15 16-18, 50 - 51 52 46
20 - 28,
48
Chapter 6
Chemistry of Water,

Chemistry in Water
Chemistry of Water, Chemistry in
Water
3
Arsenic Ain’t Arsenic
• White CuSO4(s) is converted
to blue CuSO4·∙5H2O (s) by
addi=on of water.
• Applying heat drives off the
water molecules to yield
white CuSO4(s).
• White Cu(NO3)2(s) yields a
blue solu=on when
dissolved in water.
4
• The blue colour is aIributed to absorp=on of red light by
aquated copper (II) ions. These are ions surrounded by
water molecules.
• Copper (II) ions undergo a complexa.on reac=on.
5
What does this mean for arsenic?
• Arsenic compounds can be categorized as either
inorganic arsenic or organic arsenic, depending on the
nature of the elements to which it is bonded.
• Inorganic arsenic species are toxic:
– e.g., Arsenic trioxide (As2O3), arsenic pentoxide (As2O5), the
arsenite and arsenate ions (AsO33-, AsO43-)
• Organic arsenic species are not always toxic:
– e.g., arsenobetaine is non-‐toxic:
Toxicity depends on “bioavailability”

6
The Remarkable ProperJes of Water
Density:
•Liquid water is more dense
than the ice.
•The density-‐temperature
curve shows a maximum at
4°C.
As a consequence, in winter
open water freezes on the
surface and protects the
underlying water and aqua.c
life.
7
Specific heat capacity:
•By defini=on: the amount
of heat required to raise
the temperature of 1 g of a
substance by 1 K.
•The specific heat capacity
of water is high compared
to other liquids.
8
Midterm Oct. 8, 2014, 5:00 pm
Chapters 1-‐7
Front Back
Practical 1-13, 14, 29, 30 37, 49 31 - 35 19, 47, 36, 38, 39 - 41, 42 - 45
Section 15 16-18, 50 - 51 52 46
20 - 28,
48
Enthalpy Change of VaporizaJon:
•Vaporiza=on (evapora=on) is the process in which a
substance in the liquid state changes to the gaseous state.
•Energy needs to be supplied for such process in order to
break intermolecular forces.
•The intramolecular forces (i.e., H-‐O bonds) are not broken
and both liquid and vapour are composed of H2O
molecules.
10
Enthalpy Change of VaporizaJon
Gas
Liquid
11
• Energy changes under constant
pressure condi=ons are called
enthalpy changes.
• The symbol for enthalpy is H,
and for enthalpy change is ΔH.
• The process opposite to
vaporiza=on is called
condensa/on.
• During condensa=on, energy is
removed from the system.
12
• The amount of energy required to evaporate 1 mol of a
substance is called the molar enthalpy change of
vaporiza/on (ΔvapH).
• One mole of water requires much more energy than the
same amount of other common substances with similar
size molecules.
13
EXAMPLE:
•1.00 L of water is put in a pan at 100°C. The density of
water at this temperature is 0.958 g mL-‐1.Over =me, the
water evaporates. How much energy did the water absorb
during this process?
STRATEGY:
1. Find the amount of water (number of moles) that
evaporates.
2. Use the molar enthalpy change of vaporiza=on
(ΔvapH) for water from table to calculate the total
amount of energy.
14
SOLUTION:
1.a) Mass of water, m = V × d = 1000 mL × 0.958 g mL-‐1 =
958 g
b) Amount of water, n = m/M
where M = 18.02 g mol -‐1 is the molar mass of water
n = 958 g / 18.02 g mol-‐1 = 53.2 mol
2.E = n × ΔvapH = 53.2 mol × 40.7 kJ mol-‐1 = 2.16 × 103 kJ
How does this compare to the amount of energy 1.0
mol of N2(ℓ) would absorb at its boiling point
(-‐195.8°C)?
15
Equilibrium Vapour Pressure
Water Acetone
In these two closed flasks (maintained at 25°C), pressure gauges will
show 3.17 kPa for water and 30.8 kPa for acetone, regardless of how
much liquid is present. These values are the equilibrium vapour
pressures at this temperature.
16
Equilibrium Vapour Pressure:
During vaporiza=on of water in a closed flask, as more and
more molecules occupy the vapour space, the frequency
of those returning to the liquid becomes equal to the
frequency of molecules passing into the vapour. This is
called a dynamic equilibrium and the pressure that is
reached at this point is called the equilibrium vapour
pressure.
17
Equilibrium Vapour Pressure
• The dynamic equilibrium of water is represented by a
following formula:
H2O(ℓ) ⇋ H2O(g)
• The equilibrium vapour pressure
of water is lower than other
substances whose molecules are
of similar size.
• The higher the equilibrium
vapour pressure at a given
temperature, the more vola.le
the compound.
18
Boiling Point
• The boiling point is the temperature at which the
vapour pressure of the liquid is the same as the
pressure of the atmosphere ac=ng down on the liquid
surface.
• If the atmospheric pressure is equal to 1 atm, this
temperature is called the normal boiling point.
19
Boiling Point
• The normal boiling point of water is much higher than
other liquids with similar-‐sized molecules.
20
Surface Tension
• Liquids (including water) behave as though they have a
“skin” stretched across their surface.
• The surface tension of a liquid is the amount of energy
required to increase its surface area.
21
Surface Tension
• Water has very high surface tension compared with
other liquids.
22
Intra-‐ and Intermolecular Forces
• Intermolecular forces are forces of aIrac=on between

molecules.
• Chemical changes are related to breaking and forma=on
of intramolecular forces (i.e., covalent bonds).
• Physical changes are governed by intermolecular forces.
What is the origin of intermolecular forces?
23
Bond Polarity
• Based on a previous analysis of the density, specific heat
capacity, equilibrium vapour pressure, etc… of water,
one can conclude that water has rela.vely strong
intermolecular forces.
• Experiments have confirmed that water molecules have
a dipole moment, a force that aligns them toward the
poles of an electric field.
• Water molecule is an electric dipole, with a posi=ve
charge at one end and nega=ve at the other.
24
Bond Polarity
• Two atoms that share a pair of electrons in a covalent
bond may have different ability to aIract bonding
electrons.
• This ability to aIract bonding electrons is called
electronega/vity.
• Net nega=ve charge resides on the atom with greater
electronega=vity.
• The greater the difference between the
electronega=vity of bound atoms, the greater the
charge separa=on.
25
Bond Polarity
Es=mates of electronega=vi=es of various elements:
26
Bond Polarity
EXAMPLE:
• Hydrogen fluoride
molecules have one polar
covalent bond.
• Water molecules have two
polar covalent bonds.
• Ammonia molecules have
three polar covalent
bonds.
27
Intermolecular Forces
Molecular Polarity and Dipole-‐Dipole Forces
• Water molecules have two polar covalent bonds at an
angle of 104° to each other.
• The net result is that the molecule has a dipole ac=ng in
the direc=on that bisects the H-‐O-‐H angle.
• The debye (D) is the unit for the dipole moment, µ.
28
The influence of symmetry on the polarity of
molecules with two and three bonds:
29
Dipole Moments and Geometry
30
Molecular Polarity and Dipole-‐Dipole Forces
• Polar molecules align themselves so that the posi=ve
end of one molecule is oriented toward the nega=ve
end of an adjacent molecule.
• This type of intermolacular force is called a dipole-‐
dipole force.
31
Hydrogen Bonding
Unexpectedly high boiling points of polar molecules of
certain hydrogen components indicate stronger
intermolecular forces than predicted by dipole-‐dipole
interac=ons.
32
Hydrogen Bonding
33
Hydrogen Bonding
Contribu=ons to the strength of hydrogen bonding
between water molecules:
•A hydrogen atom has only one electron, which, when
localized in the bond, leaves the posi=vely charged
hydrogen nucleus rather exposed to adjacent molecules.
•A hydrogen atom is small and can get very close to
oxygen atoms in adjacent water molecules.
34
Hydrogen Bonding
• A hydrogen atom is small and can get very close to oxygen
atoms in adjacent water molecules.
• The oxygen atom in the water molecule has two pairs of
electrons (lone pairs) not used in the bonding. These
provide localized centres of nega=ve charge that can
contribute to hydrogen bonding with adjacent molecules.
35
Dispersion Forces in All Molecular Substances
Dispersion or London forces are due to instantaneous
dipole-‐induced dipole forces. They are present in all
molecular substances.
a) Non-‐polar molecules with evenly distributed electron
cloud.
b) An instantaneous dipole in one molecule induces an
instantaneous dipole in the adjacent molecule.
c) Instantaneous dipole-‐induced dipole forces are present
throughout the surface.
36
RelaJve Strength of Various
Dispersion forces < dipole-dippole < H-bonding
37
Explaining the ProperJes of Water
Observed proper=es of water can be explained by
reference to hydrogen bonding:
1.The increase in density of liquid water between 0° and
4° can be explained by a par=al breakdown of the regular
ice structure and forma=on of close packaged water
molecules due to the hydrogen bonding, which causes the
volume to contract.
2.Remaining ice structures will completely disappear
above 4° and density decreases further due to increasing
kine=c energy.
38
Explaining the ProperJes of Water
Observed proper=es of water can be explained by
reference to hydrogen bonding:
1. High heat capacity of water, high enthalpy change of
vaporiza=on, and high boiling point can all be aIributed to
high energy, which needs to be supplied to overcome
strong hydrogen bonds.
2. High surface tension can be explained by the forces
of aIrac=on between molecules on the surface and in the
interior of the liquid. A net inward force opposes the
increase of the surface area.
39
Water as a Solvent
Terminology first:
•The solvent is the substance in which all other
substances, the solutes, are dissolved.
•Solu=ons with water as a solvent are called aqueous
solu/ons.
•The solubility of a substance refers to the concentra=on
in a solu=on when no more substance will dissolve.
40
Dissolving Ionic Salts
• When ionic substances dissolve in water, their ca=ons
and anions separate and get dispersed amongst the
water molecules.
• Polar water molecules aIract both ca=ons and anions in
such a way that the end with opposite charge to the ion
points toward it.
41
• The aIrac=on force between ions and a polar molecule
is called an ion-‐dipole forces.
• The surrounding of ions or molecules of solutes by the
molecules of solvent is called solva/on.
• In the case of water as a solvent, we use the term
aqua/on or hydra/on.
• The ion surrounded by water molecules is called an
aquated ion or a hydrated ion.
42
• When an ionic solid dissolves in water, the process is
called dissociaJon.
• In many cases, aqueous solu=ons will conduct
electricity.
• These solu=ons are called electrolytes.
• This is happening because of the presence of ions,
which can move within the solu=on, carrying electrical
charge in an electric field.
43
Water as a Solvent
PURE WATER ELECTROLYTE
44
Water as a Solvent
SolubiliJes of Ionic Compounds
45
Water as a Solvent
46
Water as a Solvent
Dissolving Molecular Substances
1. Ethylene glycol:
•dissolves in water (miscible in water)
•polar compound
47
Water as a Solvent
Dissolving Molecular
Substances
2. Motor oil (hydrocarbon):
•does not dissolve in water
(immiscible in water)
•non-‐polar compound
•dissolves in non-‐polar
solvents such as gasoline or
CCl4
48
Water as a Solvent
The driving force for dissolu.on of molecular substances
is entropy—a natural tendency for the molecules to
achieve a more probable distribu.on.
EXAMPLE:
If two similar liquids (e.g., water and methanol) are
mixed, the mixture has a more probable distribu=on of
molecules than if the liquids remain separate.
49
50
“Like dissolves like”
•The reason for the solubility of methanol (CH3OH) in
water is the existence of –OH group, which can form
hydrogen bonds with water molecules.
•The more polar groups a molecule has, the more likely
that it will dissolve in water.
•The larger the non-‐polar part, the less likely that it will
dissolve in water.
51
Methanol Butan-‐1-‐ol Propan-‐1,2-‐diol
52
IonizaJon of Molecular Solutes
• Aqueous solu=ons of some molecular substances
conduct electricity (electrolytes).
• This is due to the breaking of a bond in a molecule and
forma=on of ions, called ioniza/on.
H2O
A‒B A+(aq) + B-(aq)
• In some cases, only a frac=on of molecules is ionized
(crea=ng a weak electrolyte).
A‒B A+(aq) + B-(aq)
53
Water as a Solvent
NON-‐ELECTROLYTE WEAK ELECTROLYTE STRONG ELECTROLYTE
54
Self-‐IonizaJon of Water
• Pure water consists of a number of water
molecules in equilibrium with a small amount
of aquated hydrogen ions and hydroxide ions.
The process in which ions are obtained is called
self-‐ioniza=on of water.
H2O(ℓ) H+(aq) + OH-(aq)
55
• At 21°C the concentra=ons of both H+(aq) and
OH-‐(aq) is 1 × 10 -‐7 mol L-‐1.
• The process can be also interpreted as a reac=on
between two water molecules:
H2O(ℓ) + H2O(ℓ) H3O+(aq) + OH-(aq)
56
• H+(aq) is con=nuously changing among several
transitory species such as the hydronium ion.
H2O(ℓ) + H2O(ℓ) H3O+ (aq) + OH-(aq)
57
• Other species may include H+(aq) surrounded by
two, three, or four water molecules, such as
H9O4+.
58
Categories of Chemical ReacJon in
Water
Main Types of ReacJons:
• Precipita=on
• Oxida=on-‐reduc=on (Redox)
• Acid-‐base
• Complexa=on
59
Precipitation Reactions
Water

A precipitation reaction produces a solid deposit called precipitate
from cations and anions in a solution
EXAMPLE:
•Precipita=on of silver chloride (AgCl)
ATrac.on between ions to form an ionic laUce competes
with aTrac.on of water molecules to the ions to keep the
ions aquated and in solu.on
Ag+(aq) + Cl-(aq) → AgCl(s)
60
Water
PrecipitaJon ReacJons
ATrac.on between ions to form an ionic laUce competes
with aTrac.on of water molecules to the ions to keep the
ions aquated and in solu.on
Some ions will not precipitate (e.g., K+(aq) and NO3-‐(aq)
ions), indica=ng that the aqua=on of ions outweighs the
aIrac=on between them. These ions are called spectator
ions.
61
Water
EXAMPLE:
•Are any insoluble products formed when
aqueous solu=ons of silver nitrate and potassium
chromate are mixed?
Solu/on:
1.Visit the guidelines to predict the solubility of
ionic compounds.
62
Water
EXAMPLE:
•Are any insoluble products formed when
aqueous solu=ons of silver nitrate and potassium
chromate are mixed?
63
Water
SOLUTION:
1.Visit the guidelines to predict the solubility of ionic
compounds.
2.Silver nitrate and potassium chromate are both soluble:
H2O
AgNO3(s) Ag+(aq) + NO3-(aq)
H2O
K2CrO4(s) 2 K+(aq) + CrO42-(aq)
3.Possible precipitates Ag2CrO4 or KNO3.
64
Water
4. Silver chromate will be formed and the balanced
equa=on is:
2 Ag+(aq) + CrO42-(aq) Ag2CrO4(s)
5. K+(aq) and NO3-(aq) are spectator ions.
65
Water
OxidaJon-‐ReducJon ReacJons
•During oxida=on-‐reduc=on (redox) reac=ons, electrons
are transferred from one species to another.
EXAMPLE:
•Oxida=on of copper metal by aquated silver ions.
66
Water
67
Water
• The reactant that takes electrons is reduced (Ag+). It is
an oxidizing agent.
• The reactant that loses electrons is oxidized (Cu). It is a
reducing agent.
The reac.on in the opposite direc.on will not happen. Ag+
ions are more strongly compe..ve for electrons than
Cu2+ ions—they have a higher reduc/on poten/al.
68
Common Oxidizing and Reducing
Agents
•NO(g) is mainly produced with dilute HNO3 solutions, whereas NO2(g) is the main product
in concentrated solutions. 69
Water
70
Water
Common approach to analysis of redox reac=ons is
to write them in form of two half-‐reac.ons:
71
Water
EXAMPLE:
•The oxida=on of zinc in hydrochloric acid
solu=ons separated into two half-‐reac=ons:
Zn(s) + 2 H+(aq) Zn2+(aq) + H2(g)
1. Zn (s) Zn2+ (aq) + 2 e-

2. 2 H+(aq) + 2 e- H2(g)
72
Water
Acid-‐Base ReacJons
• Acids are electrolytes that form hydronium ions in
the ioniza=on reac=on with water.
• Bases are compounds that have higher
concentra=ons of hydroxide ions than water as a
consequence of the ioniza=on reac=on with water.
• Acids and bases react in aqueous solu=on by transfer
of protons (H+) from the acid to the base. The
reac=on is called acid-‐base neutraliza/on.
73
Water
Acid-‐base reac.ons are compe..on of species for
H+ ions
•One model that describes acid-‐base reac=ons is that of
Brønsted-‐Lowry:
•An acid is a species from which an H+ ion is taken (proton
donor).
•A base is an acceptor of an H+ ion (proton acceptor).
74
Water
• Strong acids and bases are strong electrolytes
Common strong acids and bases:
75
Water
• Weak acids and bases are weak electrolytes.
Common weak acids and bases:
76
Water
ComplexaJon ReacJons
•Complexa=on reac=ons involve bonding to species with
lone pairs. Products are complex ions.
EXAMPLE:
77
Water
•The analysis of complexa=on reac=ons leads to a more
general acid-‐base model called the Lewis acid-‐base model.
•The lone pair donor is called a Lewis base or ligand.
•The recipient of the electron pair is called a Lewis acid.
•The product of an acid-‐base reac=on in the Lewis model
is called an acid-‐base adduct.
78
Water
79
Water
•Complexa.on reac.ons are compe..on between Lewis
bases.
Aquated Metal Ions
•Complexa=on reac=ons of aquated metal ions are the
result of compe==on between water and other Lewis
bases to bond with the metal.
80
Water
81
Water
Summary:
82
SoluJon ConcentraJon
The concentra=on of a solute represents the amount of
solute in a specified quan=ty of solu=on.
•Amount concentra=on (molarity) is the amount of solute
per litre of solu=on:
c = amount
of solute (mol)
volume of solu=on (L)
•The concentra=on of par=cular species in solu=on,
indicated by the symbol [species], may be different from
the solute concentra=on.
83
Midterm Oct. 8, 2014, 5:00 pm
Chapters 1-‐7
Front Back
Practical 1-13, 14, 29, 30 37, 49 31 - 35 19, 47, 36, 38, 39 - 41, 42 - 45
Section 15 16-18, 50 - 51 52 46
20 - 28,
48
How much energy is required to bring 18 g of liquid water from 90°C to
vapour at 100°C ? (c = 4.18 J K-‐1 g-‐1 & ΔvapH = 40.7 kJ mol-‐1)
1. 41.5 kJ mol-‐1

2. 794 kJ mol-‐1
3. 0.752 kJ mol-‐1
4. 85.6 kJ mol-‐1
5. 12.2 kJ mol-‐1
Since the vapour pressure of water ≠ 0, puddles can dry
at ambient temperature.
1. True
2. False
Which of the following bonds would have the highest polarity?
1. S-F
2. C-Cl
3. H-C
4. N-O
5. P-I
Since CH2Cl2 is symmetrical, there would be no net dipole
moment.
1. True
2. False
Which of the following molecules would be non-‐polar?
1. PCl3
2. H2O
3. NH3
4. HCl
5. BF3
Which of the following molecules would have the weakest
intermolecular forces?
1. H2
2. CH4
3. HCl
4. NH3
5. H2O
TheoreJcally, applying an electrical current to a person in a
bathtub filled with pure water is safe.
1. True
2. False
A soluJon contains K+, NH4+, Ca2+, SO42-‐, and ClO4-‐. What
salt would precipitate?
1. K2SO4
2. Ca(ClO4)2
3. (NH4)2SO4
4. KClO4
5. CaSO4
High-‐tech electronics can be submerged in pure water as a means to
effecJvely cool them without causing any “shorJng.”
1. True
2. False
As the chain length of an alcohol increases, the solubility in water
would also increase.
1. True
2. False
In the following reacJon, Zn is acJng as the reducing agent.
Zn(s) + Cu2+(aq)  Zn2+(aq ) + Cu(s)
1. True
2. False
A strong acid is also considered a strong electrolyte.
1. True
2. False
AddiJon of vinegar to baking soda would be considered an acid
base reacJon.
1. True
2. False

1st Year Chemistry Lecture 6

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1st Year Chemistry Lecture 6

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Midterm

Oct. 8, 2014, 5:00 pm

Chemistry of Water,

Toxicity depends on “bioavailability”

• Intermolecular forces are forces of aIrac=on between

What is the origin of intermolecular forces?

Dispersion forces < dipole-dippole < H-bonding

PURE WATER ELECTROLYTE

Methanol Butan-‐1-‐ol Propan-‐1,2-‐diol

A‒B A+(aq) + B-(aq)

H2O(ℓ) H+(aq) + OH-(aq)

H2O(ℓ) + H2O(ℓ) H3O+(aq) + OH-(aq)

H2O(ℓ) + H2O(ℓ) H3O+ (aq) + OH-(aq)

Ag+(aq) + Cl-(aq) → AgCl(s)

2 Ag+(aq) + CrO42-(aq) Ag2CrO4(s)

5. K+(aq) and NO3-(aq) are spectator ions.

1. Zn (s) Zn2+ (aq) + 2 e-

1. 41.5 kJ mol-‐1

You might also like

1st Year Chemistry Lecture 6

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

1st Year Chemistry Lecture 6

Uploaded by

Copyright:

Available Formats

Midterm

Oct. 8, 2014, 5:00 pm

Chemistry of Water,

Toxicity depends on “bioavailability”

• Intermolecular forces are forces of aIrac=on between

What is the origin of intermolecular forces?

Dispersion forces < dipole-dippole < H-bonding

PURE WATER ELECTROLYTE

Methanol Butan-­‐1-­‐ol Propan-­‐1,2-­‐diol

A‒B A+(aq) + B-(aq)

H2O(ℓ) H+(aq) + OH-(aq)

H2O(ℓ) + H2O(ℓ) H3O+(aq) + OH-(aq)

H2O(ℓ) + H2O(ℓ) H3O+ (aq) + OH-(aq)

Ag+(aq) + Cl-(aq) → AgCl(s)

2 Ag+(aq) + CrO42-(aq) Ag2CrO4(s)

5. K+(aq) and NO3-(aq) are spectator ions.

1. Zn (s) Zn2+ (aq) + 2 e-

1. 41.5 kJ mol-­‐1

You might also like

Methanol Butan-‐1-‐ol Propan-‐1,2-‐diol

1. 41.5 kJ mol-‐1