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1/10/2018

UNUSUAL PROPERTIES of WATER


1. HIGH VISCOSITY
• = resistance to flow
• Increases with strength of forces, decreases
with temperature (see Table)
CHM 116 Spring 2018 2. HIGH SURFACE TENSION
• = energy required to increase surface area
Ch. 11 Part 2:
• Molecules on surface have fewer surrounding
Unusual Properties of Water molecules and attractions = less stable
Phase Diagram; Vaporization and Fusion • In air, water forms drops to minimize surface
area
• High enough for water so insects can walk on
its surface
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MORE UNUSUAL PROPERTIES of WATER : Capillary Action MORE UNUSUAL PROPERTIES of WATER: DENSITY
3. CAPILLARY ACTION
• = ability of liquid to flow up narrow
tube 4. DENSITY of LIQUID > DENSITY of SOLID
• Results when attraction to surface
(adhesive force) >attraction to self • Most substances show opposite behavior
(cohesive force) • Due to basic structure of common ice crystal: consists of hexagonal rings of H-
• In glass (which is polar), water forms bonded water molecules which can attach to each other and stack. (See
convex meniscus (illustrated at right illustration next slide.)
with water dyed red)
• When ice melts, some H-bonds break, allowing structure to collapse on itself,
• In nonpolar plastic, water forms increasing the density
concave meniscus (as does mercury in
all containers, since mercury has vey • Expansion of water on freezing produces frostbite and freezer burn, as well as
strong cohesive forces-illustrated at weathering of rocks and production of potholes!
right)

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Basic Hexagonal Ring Structure of Most Common Form of Ice More Unusual Properties of Water: High Heat Capacity
5. High Heat Capacity and Specific Heat
• Heat capacity is a physical property measuring the
ability of material to store heat. (See Ch. 6.)
• Depends only on identity and state of material, and
on conditions (T, P).
• Can be expressed as either per MOLE (molar heat
capacity) or per GRAM (specific heat, Cs ).
• Used to calculate the amount of heat involved
when a substance is heated or cooled:
Q = q = heat = Cs x mass x DT
• Water is able to store heat in its hydrogen bonds,
giving it an unusually high Cs value ( it is an
INSULATOR); so changes T slowly when heated.

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MORE UNUSUAL PROPERTIES of WATER: Heat of Vaporization MORE UNUSUAL PROPERTIES of WATER: Heat of FUSION
6. HIGH HEAT of VAPORIZATION 7. HIGH HEAT of FUSION
• Recall from Ch. 6, heat of vaporization (DHvap ) = amount of energy needed to • Recall from Ch. 6, heat of fusion (DHfus ) = amount of energy needed to melt given
vaporize given amount (usually 1 mole or 1 gram) at its normal boiling point. amount (usually 1 mole or 1 g) of solid at its normal melting point. (Note error in
Table 11.8: These are DH fus , not DHvap !)
• Always endothermic, as energy is absorbed to break all remaining intermolecular
forces when turning liquid to gas. • Always endothermic, as energy is absorbed to break some intermolecular forces
when turning solid to liquid.
• Water’s is unusually high (compared to molecules of similar size) due to strong H-
bonds that must be broken. • Water’s is unusually high (compared to molecules of similar size) due to strong H-
bonds that must be broken.

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REVIEW: Calculating Heat for T Changes and Changes of State Vapor Pressure
1. How much heat is released when 100. g of liquid water at normal • Above any liquid, some molecules have enough
boiling point (100o C) and 1.00 atm comes in contact with and cools energy to escape and are present as gaseous vapor.
to the T of skin (37o C?) • In open container, rate of evaporation is greater than
rate of condensation, so volume of liquid decreases
until air is SATURATED
• In closed container, eventually rates become EQUAL,
2. How much additional heat is released when 100. g STEAM at 110o C setting up a DYNAMIC EQUILIBRIUM where the
comes into contact with skin at 37o C? (Note: can’t cool steam concentration of vapor becomes CONSTANT with
below its condensation point without condensing. ) time. The partial pressure of this vapor = VAPOR
PRESSURE.
Cs (steam) = 2.01 J / g x o C, DHcond = - DHvap at 100o C • At a given temperature, water has a low vapor
pressure due to stronger forces in the liquid.

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Vapor
VAPOR PRESSURE Pressure
and BOILING & Boiling Pt
POINT VAPOR PRESSURE and BOILING POINT
In an Open Container, Vapor Pressure is Countered by Atmospheric Pressure. • For any liquid, vapor pressure
Atmospheric Pressure increases with temperature. (Why?)
• When vapor pressure = external
pressure, the liquid BOILS. (In an open
container, this is when vapor pressure
= atmospheric pressure.)
As the Temp. Increases ⇒ Vapor Pressure Increases.
• Substances such as water with low
vapor pressures at a given T, require
more heating is required to boil, so
have higher boiling points.
The Temp. (of a Liquid) where the Vapor Pressure Equals the Pressure of the • If the external pressure increases, the
Atmosphere is the Boiling Point Temp. of the Liquid. boiling point increases, (WHY?)
• Normal boiling point is at standard
Note, As Atmospheric Press. Decreases with Altitude, atmospheric pressure of 1 atm.
Bp also decreases at Higher Altitudes.
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Dependence of Boiling Point on Pressure


EXAMPLE: Using the Clausius-Clapyron Equation
• The Clausius-Clapyron allows calculation
of the pressure dependence of the If only two pressure-temperature points are used, the two point version of the
boiling point Clausius-Clapyron Equation can be used.
• The equation actually gives the T P DH 1 1
dependence of the vapor pressure ln P2 – ln P1 = ln ( 2 ) = - ( vap ) ( - )
1P R 2 T T
1
DH 1 Example: The normal boiling point of water (at P = 1.0 atm) is 100o C. What is the
ln Pvap = -[ ( vap )( )] + ln b
R T boiling point in Denver, where the pressure is 83% that at sea level? Note DHvap of
Here, R = 8.314 J/(mole ● K) water = 40.7 kJ/mole. (Remember, T must be in KELVIN!!)
T = temp. in KELVIN
DHvap = Heat of Vap. in Joules/mole
The constant b is obtained from the y-
1
intercept of the graph of ln Pvap vs. (Can also use the CC equation to get DHvap , if know the vapor pressure at two
T
Note if Pvap = external P, then T = boiling different temperatures.)
point at that pressure
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HEATING CURVE for WATER


HEATING and COOLING CURVES for pure substances
Heating Curve = Plots of Temperature vs. Time (or vs. heat added) as
material is steadily heated or cooled.
• For PURE WATER, idealized heating curve is on the next page
• Allows determination of melting point and /or boiling point
• Reverse of heating curve = cooling curve.
For pure substance, boiling point = condensation point
and melting point = freezing point
• If substance is NOT PURE, different components in the mixture have different
melting and boiling points. Melting will begin at a lower temperature than if pure
(freezing point depression-see Ch. 12) and occur over a range of T. (Wider range =
more impurities. Likewise boiling point begins at a higher T (boiling point
elevation-See Ch. 12) and occurs over a range of T, depending on impurities.
Thus measurement of boiling or melting point can be used to assay sample purity.

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PHASE DIAGRAMS for PURE SUBSTANCES SIMPLIFIED PHASE DIAGRAM of WATER (Fig. 11.31)
A PHASE DIAGRAM is map of the T and P regions where various phases
exist. Fig. 11.31 shows the idealized phase diagram for water, Fig.
11.32 shows carbon dioxide.
PARTS of a PHASE DIAGRAM
1. Main Regions (s, l, g) = where that phase is stable. GAS PHASE dominates at
highest T and lowest P, and SOLID at lowest T.
2. Boundary Lines = where phases on either side coexist (are in equilibrium).
- FUSION CURVE (solid-liquid) can use to give melting pt. at different P’s. Note
WATER’S has an unusually NEGATIVE slope due to the higher density of
liquid compared to ice. (Compare to the fusion curve on the phase diagram
for carbon dioxide on the following page.)
-VAPORIZATION CURVE (liquid-gas) gives dependence of boiling pt. on P.
-SUBLIMATION CURVE (solid-liquid) gives dependence of the sublimation pt.
on P. Note that water will sublime (convert directly from solid to gas) only
at reduced pressures.
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PHASE DIAGRAMS: Critical Point and Triple Point PHASE DIAGRAMS: Multiple Solid Phases
CRITICAL POINT The previous phase diagram for water was
oversimplified in that it only showed a single solid
• Where vaporization curve ends. phase.
• Above this T (critical T) and P (critical Water actually has multiple solid phases. The most
P), separate gas and liquid phase do common solid phase (Ice I) predominates around
not exist, only “supercritical fluid”. standard P.
• Cannot condense gas to liquid at T > Other phases show up at elevated pressures. (See
critical T simply by applying pressure. the phase diagram at right.)
• Characteristic of substance. Note if there is more than one solid phase,
TRIPLE POINT multiple triple points exist! However, NO MORE
THAN 3 PHASES of ANY time can coexist at a given
• T, P at which 3 phases can coexist. T, P.
• Unique for each substance.

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