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Unit 5 (Chp 11,13)
Bonds & IMAFs inLiquids, Solids, and
SolutionsJohn D. Bookstaver
St. Charles Community College
St. Peters, MO
2006, Prentice Hall, Inc.
Chemistry, The Central Science, 10th editionTheodore L. Brown; H. Eugene LeMay, Jr.; and Bruce E. Bursten
Attractions
Intra–(strong)
Inter–(weak)
“Bonds” “IMAFs”
??
?
Ionic(metal–
nonmetal)
Covalent(nonmetals)
polarnon-polar
Intermolecular Attractive ForcesIntramolecular Attraction (within)
(strong bonds)
(weak)Intermolecular Attraction (between)
Which attraction is overcome (broken) by melting & vaporizing? weak IMAFs
between molecules
Intermolecular Attractive Forces
IMAFs determine physical properties such as boiling & melting points, vapor pressure, and viscosity.
bp, mp, vp, visc.
Intramolecular Attraction (within) (strong bonds)
(weak)Intermolecular Attraction (between)
States of MatterThe main difference between phases of matter is the distance between particles.
changes of state
States of MatterState (distance between particles) at a certain
T and P depends on two opposing qualities:
IMAFs(intermolecular attractive forces
between particles)
KE(kinetic energy of the particles
vs.
Attractions
Intra–(strong)
Ionic(metal–
nonmetal)
Covalent(nonmetals)
polar non-polar
Inter–(weak)
“Bonds” “IMAFs”
?
At that instant, the He atom is polar (instantaneous dipole).
(excess of e–’s on one side, and shortage on the other)
Electrons in the 1s orbital of He repel each other, BUT…
they occasionally wind up on the same side of the atom.
London Dispersion Forces
d- d+
London Dispersion Forces
instantaneous dipole
induced dipole
causes
LDFs:attractions between instantaneous dipoles and induced dipoles caused by motion of e–’s.
d- d+
d- d+
London Dispersion Forces• present in all molecules,
(polar & nonpolar)
• The tendency of an electron cloud to distort to become temporarily polar in this way is called ___________.polarizabilityd- d+ d- d+
Factors Affecting London Forces
• LDFs increase with increased MW b/c…
larger e– clouds, are more polarizable.
(use this phrase to answer FR question)
MW (molecular weight)
Factors Affecting London Forces
• long, skinny molecules have stronger IMAFs due to……increased surface area to form more attractions.
(SAcylinder > SAsphere)
Shape
Attractions
Intra–(strong)
Ionic(metal–
nonmetal)
Covalent(nonmetals)
polar non-polar
Inter–(weak)
“Bonds” “IMAFs”
?London
dispersion forces
(nonpolar & all)
Dipole-Dipole Interactions
• Polar molecules with permanent dipoles are attracted to each other.
(dipole) (dipole)
Dipole-Dipole Interactions
The more polar the molecule,the higher the boiling/melting point.
(due to greater dipole-dipole IMAFs that require more energy to overcome)
?
DEN
polar bonds
assym. shape
Which Have a Greater Effect:Dipole-Dipole Interactions or Dispersion Forces?
•dipole–dipole interactions (permanent dipoles) are typically stronger than LDFs (temporary dipoles as instantaneous–induced).
•But much larger molecules could have LDFs that are stronger than dipole-dipole interactions.
(larger e– clouds, are more polarizable)
Attractions
Intra–(strong)
Ionic(metal–
nonmetal)
Covalent(nonmetals)
polar non-polar
Inter–(weak)
London dispersion
forces(all, nonpolar)
dipole–dipole(polar)
“Bonds” “IMAFs”
?
nonpolar
polar
Boiling Points
How Do We Explain This?
•unusually high bp•unusually strong IMAFs
• H-bonds are caused by an electron deficient H atoms (bonded to N, O, or F) attracted tosmall, very electronegative N, O, or F atoms on a nearby molecule.
Hydrogen Bonding
Attractions
Intra–(strong)
Ionic(metal–
nonmetal)
Covalent(nonmetals)
polar non-polar
Inter–(weak)
London dispersion
forces(all, nonpolar)
dipole–dipole(polar)
H–bondsH with N, O, F?
“Bonds” “IMAFs”
Ion-Dipole Interactions• ionic solutes dissolve in polar solvents
OH
H
OH
H
Na+ Cl–
Attractions
Intra–(strong)
Ionic(metal–
nonmetal)
Covalent(nonmetals)
polar non-polar
Inter–(weak)
London dispersion
forces(all, nonpolar)
dipole–dipole(polar)
H–bondsH with N, O, F
ion–dipole(aq ions)
“Bonds” “IMAFs”
Intermolecular Attractive Forces
Stronger
Weaker
H-bonds(if H with N, O, or F)
dipole-dipole int.’s(polar molecules)
London dispersion forces(nonpolar, instant–induced dipoles)
• London dispersion forces (LDFs) only• bp increases as length of chain b/c…
…larger e– cloud, more polarizable
Organic Functional Groups
Alkanes
polar & H-bond
polar
Organic Functional GroupsWhat IMAFs?
Organic Functional GroupsWhat IMAFs?
polar
polar
polar
polar
& H-bond
& H-bond
H-bond
3–pentanone(ketone)
propanal (aldehyde)
ethylamine(amine)
ethanoic acid (carboxylic acid)
trimethylamine(amine)
dipole-dipole
dipole-dipole
dipole-dipole
H-bondbutane(alkane)
LDFs
ethanol(alcohol)
H-bond
IMAFs in Protein Structure & DNA
aminoacid
H bonds
IMAFs in Protein Structure & DNA1
23
4H
bonds
IMAFs in Protein Structure & DNA
H-bonds H-bonds
HWp. 476
Intermolecular Forces Affect Many Physical Properties
The strength of the attractions between particles can greatly affect the physical properties of a substance or solution.
Cohesive• to each other
Adhesive• to surface
Cohesive/Adhesive Forces
cohesive
adhesive
glass
Capillary Action
• due to co/adhesive forces
results from thenet inward force experienced by the molecules on the surface of a liquid.
Surface Tension
• resistance of a liquid to flow
• increases with IMAF’s and decreases with higher temp.
Viscosity
HW p. 479 #29
Phase ChangesHW p. 479
#34
• Heat of Fusion (Hfus): energy to change (s) to (l) at melting point.
Energy and Phase Changes
Energy and Phase Changes
• Heat of Vaporization (Hvap): energy to change (l) to (g) at boiling point.
DEMO: butane
What happens to added KE?
Temp. does not change during phase change.
Energy and Phase Changes
Added energy
separates particles
(overcome IMAFs)
HWp. 480
#3547a
liquid molecules escape to vapor
Vapor Pressuremore volatile
=more vapor
pressure above liquid
gas molecules condense to liquid
(dynamic equilibrium)
=_____ IMAFSweak
Vapor Pressure• As T ↑, the fraction of molecules that have
enough energy to escape increases.
As more molecules escape the liquid, the pressure they exert increases.
Dynamic Equilibrium:vaporize/condense at same rate
Vapor Pressure
Vapor Pressure
•boiling point:T at which
vapor pressure=
atmospheric pressure
•normal b.p.:T at which
v.p. = 1 atm
HW p. 480 #47b, 48
DEMO: boil H2O
Solutions• homogeneous mixtures of
pure substances.• solute is dispersed uniformly
throughout the solvent.
+
Why does stuff dissolve?
IMAFs betweensolute–solvent
must be stronger
IMAFs between solute–solute
solvent–solventsolvated
(dissolved)
For Ionic Solutes…
Ions are soluble in water because ion-dipole attractions are strong enough to overcome the crystal lattice energy of the ionic solid salt.
Energy Changes in Solution
separation of solute(absorb = endothermic)
separation of solvent(absorb = endothermic)
attractions between solute and solvent(release = exothermic)
H
Demo
+
+ +
+
+–
–
–
enthalpy(heat)
∆H(final – initial)
Why Do Endothermic
Processes Occur?
Usually favorable processes tend to lower energy. ∆E = – (exo or release)
But in some processes, heat is absorbed, not released.
+
+
+
–
How?
EntropyEntropy (S):
∆S = (final – initial)
∆S = (more – less)
∆S = +
• increasing the entropy (dispersal) by mixing lowers the energy of a system (even if ∆H = +).
(less disorder) (more disorder)
∆H + (heat absorbed)
25oC 25oC 10oC∆E + (raised)
∆S + (gains disorder)
∆E – (lowered)
(disorder or randomness)dispersal of matter & energy
Types of Solutions
• SaturatedSolvent holds
maximum solute possible at that temperature.
Dissolved solute is in dynamic equilibrium with solid solute particles.
• UnsaturatedLess than the
maximum dissolved at that temperature.
Types of Solutions
• SupersaturatedMore solute than is normally possible
at that temperature.unstable; crystallization is stimulated
by a “seed crystal” or scratching.
Types of Solutions
Factors Affecting Solubility
• “like dissolves like”: (similar IMAFs)
Polar substances dissolve in polar solvents.
H2O CH3Cl CH3CH2OH NH3
Nonpolar dissolve in nonpolar solvents.
C6H14 CCl4 I2
similar IMAFs are more soluble.
Which is more soluble in water (H2O) and which is more soluble in hexane (C6H14)
HW p. 566 #12,14,18
Gases in Solution
• In general, the solubility of gases in water increases with increasing size. …WHY?
• Larger molecules have larger e– clouds stronger dispersion forces.
Gases in Solution• The solubility of gas in liquid is
directly proportional to pressure.
Gases are more soluble:
Low THigh P
1) Highest solubility at 20oC? 30oC?
solubility of solids inc. with temp.Solubility
Curves
HW p. 566 #20,23,25
2) How many grams KClO3 at 70oC ?
3) Is 50 g of KCl at 50oC sat, unsat, or supersat?
30 g of NaCl at 30oC?
The greater the IMAFs,…
the _______ the bp and mp.
the _______ the cohesion/adhesion.
the _______ the surface tension.
the _______ the viscosity.
the _______ the vapor pressure (volatility)
Intermolecular Forces Affect Many Physical Properties
greater
greater
greater
greater
lower
Which has a higher boiling point? Explain.
CF4 vs. CH3OCH3
CF4 has London dispersion forces and
CH3OCH3 has dipole-dipole interactions.
Stronger intermolecular attractive forces in
CH3OCH3 require more energy to overcome.
Intermolecular Forces Affect Many Physical Properties
Attractions
Intra–(strong)
Ionic(metal–
nonmetal)
Covalent(nonmetals)
polar non-polar
Inter–(weak)
London dispersion
forces(all, nonpolar)
dipole–dipole(polar)
H–bondsH with N, O, F
ion–dipole(aq ions)
“Bonds” “IMAFs”
mp’s & bp’smp’s (of solids)
4 Types of SolidsIonic [metal–nonmetal]
• ions (transferred e–’s)
Covalent [nonmetals]• sharing of e–’s
Covalent Network [C(d)]• shares e–’s throughout
Metallic [metals]• metal atoms bonded
by a sea of e–’s
Diamond
Quartz
Ionic Solids
• Strong Ionic Bonds in a crystal lattice of +/– ions bonded by electrostatic attraction.
hard and brittlehigh melting pointsconduct in solution(aq) or molten(l)
(Coulombic)
(ordered)
E = q1q2
d
stronger attraction
more q
less d
more energy
to break
Covalent (Molecular) Solids
• Weak IMAF’s (LDF’s, dipole-dipole, H-bonds)softerlower melting points
C(graphite)
Covalent-Network Solids
• Strong Covalent Bonds throughout.C(diamond) WC2 (carbide) SiO2 (quartz)
Very hardVery high melting points
C(graphite) C(diamond)
Metallic Solids• Metals are not
covalently bonded, but attractions are too strong to be IMAFs.
• Metallic Bondsdelocalized valence “sea” of electrons.Excellent conductorsMalleable and Ductile (“smooshable”)soft to very hardlow to very high m.p.’s
Alloys
Alloys:Homogeneous metallic mixtures (solutions) by mixing melted metals in the liquid phase.
Brass Steel
67%Cu, 33%Zn80%Fe, 0.4%C, 18%Cr, 1%Ni
Attractions:Held together mainly by metallic bonding due to a delocalized sea of electrons.
AlloysBrass Steel
• at. radius = similar• density = in between• malleability = similar
Substitutional:• at. radius = different
(smaller fits between larger)
• density = greater(more mass in same volume)
• malleability = less
Interstitial:
Fe Fe Fe Fe
Fe Fe Fe
Fe Fe Fe Fe
C
Attractions in Solids, Liquids, & Solutions
Molecular
Covalent-Network
Ionic
Metallic Metallic Bonds“sea” of electrons
SoftLow mp & bpPoor conductor
Very hardVery high mpPoor conductor
Hard and brittleHigh mpConducts as (aq) or (l)
Soft to very hard Low to very high mp
Great Conductor, Malleable, Ductile
Ar I2 CO2 H2O C2H5OH
C11H22O11C(diamond)
SiO2
WC2
NaClCuSO4
All metals& alloys: Cu, Fe, K, Al,…
Covalent Bonds (network)C(diamond) , SiO2 (quartz) ,WC2 (tungsten carbide) , etc…Ionic Bondscrystal lattice of charged ions
Intermolecular Attractions (IMAFs)London dispersion forcesDipole-dipole interactionsHydrogen bonds
Type Forces Between Particles Properties
d-
d+
- +
Solutions Solute-Solvent Attractionssimilar IMAFs or ion–dipole
(l) + (l),(s) + (l) = (aq)
q1q2
d
(nonpolar)(polar)
(H with N, O, F)
Molecular (IMAFs)
Hydrogen bonds(if H with N , O , or F)
Dipole-dipole interactions(polar molecules)
London dispersion forces(all molecules & nonpolar)instant/induced dipoles)
Ionic Bonds(attractions between +/– ions)
Attraction or Bond Stronger with:
greater ∆ENN < O < F
greater ∆ENgreater dipole moment
larger e– cloud,more polarizable
greater q, less d(Coulombic attraction)
Molecular (IMAFs)
The Stronger the Attractions, the…
higher mp of solid.
harder solid.
higher bp of liquid.
higher viscosity of liquid.
lower vapor pressure of liquid (more volatile).
more soluble in solutions (similar attractions).
Attractions Affect Physical Properties
Reasoning with Concepts
1) Identify attractions(Bonds? IMAFs?)
2)Compare strength
3)Connect to energy (abs./rel.)and/or physical property
+ –