Ch1_L11-2nd 2016-2017 J
Chem 1
Molecular Geometry
2nd Sem 2016-2017
Lecture 11
FCariño
Comparison of Dipole Moments
VSEPR Geometries (Polarity)
Dichloromethane
Carbon tetrachloride
m=0D m = 1.62 D
sp2 hybridization
Orbital hybridization • One s orbital + two p orbitals à three
http://www.mhhe.com/physsci/chemistry/essentialchemistry/flash/hybrv18.swf
• One s orbital + three p orbitals à four equivalent sp2 hybrid orbitals, directions as
equivalent sp3 hybrid orbitals, shown
directions as shown • Number of hybrid orbitals formed dependent
• Number of hybrid orbitals formed on number that participated in the
dependent on number that hybridization process (1 + 2 = 3)
participated in the hybridization
process (1 + 3 = 4)
http://www.mhhe.com/physsci/chemistry/essentialchemistry/flash/hybrv18.swf
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sp hybridization
sp3d hybridization
• One s orbital + one p orbitals à two http://www.mhhe.com/physsci/chemistry/essentialchemistry/flash/hybrv18.swf
equivalent sp hybrid orbitals, directions as
shown
One s orbital
• Number of hybrid orbitals formed dependent
Three p orbitals
on number that participated in the
One d orbital
hybridization process (1 + 1 = 2)
http://www.mhhe.com/physsci/chemistry/essentialchemistry/flash/hybrv18.swf
sp3d2 hybridization
http://www.mhhe.com/physsci/chemistry/essentialchemistry/flash/hybrv18.swf
One s orbital
Three p orbitals
Two d orbitals
http://www.mhhe.com/physsci/chemistry/essentialchemistry/flash/hybrv18.swf
Carbon’s valence shell Ethene, 3 sp2, 1 p
http://www.mhhe.com/physsci/chemistry/essentialchemistry/flash/hybrv18.swf
• C has 3 attached
groups
• sp2: 33% s and
67% p character
•bond angles 120o relative to each other
• each sp2 hybrid involved in a s bond, p
↑ ↑ orbital in a p bond
↑ ↑ •double bond = 1s + 1p bond
two sp and two p http://www.mhhe.com/physsci/chemistry/carey5e/Ch02/ch2-3-2.html
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Ethyne, 2 sp, 2 p Ethyne, 2 sp, 2 p
• Both C’s sp hybridised (50% s, 50% p)
•2 C-H bonds made by sp of C and s of H (red) à σ •2 sp hybrids point in opposite directions at
•1 C-C s bond made sp of 1C with sp of the other C 180o relative to each other
(green) àσ •each sp hybrid involved in a σ bond p orbitals
• 2 C-C bonds are made by the interaction of the 2 forms the 2p bonds
p orbitals of C’s (black) à p •triple bond = 1σ + 2p bonds
http://www.mhhe.com/physsci/chemistry/carey5e/Ch02/ch2-3-3.html http://www.mhhe.com/physsci/chemistry/carey5e/Ch02/ch2-3-3.html
Diamond Graphite
•Carbon atoms
arranged in hexagon
• All C atoms
•Layers held together by
• Repeating unit is weak forces that slip
tetrahedral past one another
• C connected by •Good lubricant
covalent bonds
•Soft enough to leave
• Very hard and rigid trace
Properties of Matter in Bulk
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3 States of matter 3 States of matter
• Units of matter in constant motion
• Solid - definite shape and volume.
• State of matter dependent on speed of motion and
• Liquid - definite volume but take shape of attractive forces that exist among these units à
container determine extent of spaces between units of matter
• Gas - no definite shape or volume; expand
to fill container.
Gases Kinetic Molecular Theory of Gases
•Indefinite shape and indefinite volume
•Gases made up of tiny, invisible, particles
•↑ higher temperature, faster gas particles called molecules separated by great distances
move, larger volume of space occupied. •Gases in constant, random and straight line
•May be elements or compounds motion.
•Gas molecules collide with one another and
•May be with walls the container à pressure
• Monoatomic: He, Ne, Ar, Kr, Xe, Rn •Collisions are completely elastic: total energy
• Diatomic: H2, O2, N2, CO, Cl2 remains constant (none lost due to collision)
• Triatomic: CO2, O3, NO2, SO2, H2S •Kinetic energy of gas molecules directly
• Tetratomic: NH3, C2H2, PH3 proportional to absolute temperature (oK
scale).
• Pentatomic: CH4, CH3Cl
Properties describing physical gas
Pressure behavior
• Gases exert pressure on walls of container.
• Based on kinetic molecular theory, any surface
• Amount of gas (moles)
in contact with gas constantly bombarded by gas • Volume (Liters or milliliters)
particles. • Pressure (atmosphere ; 1 atm = 760 mmHg
• At each collision, molecule moving with = 101 kPa)
momentum mv strikes surface.
• Elastic collisions à molecule bounces back with
• Temperature (Kelvin; K = oC + 273.15)
same velocity in opposite direction with no loss • Freezing point of water = 0 oC = 273.15 oK
of energy • Boiling point of water = 100 oC = 373.15 oK
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Absolute zero
• 0 oK = -273.15 oC = absolute zero
• In classical kinetic theory, molecules
cease to move at 0 oK (experimental
evidence shows otherwise)
Gas laws
• impossible to reach (but can be
approached)
• 2003: MIT researchers set new record
of 0.45 nK (4.5 x 10-9 oK)
Boyle’s law Boyle’s Law
• Robert Boyle, 1662
• For a fixed amount of gas held at
constant temperature (T), gas
volume(V) is inversely proportional to
gas pressure (P).
PV = c (constant)
P1V1 = P2V2
http://www.grc.nasa.gov
Charles’ law Charles’ Law
• At constant pressure, the volume and
absolute temperature of a certain quantity
of a gas are directly proportional.
T = Constant x V V1 V2
V = Constant x T =
V/T = Constant T1 T2
http://www.grc.nasa.gov
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Equation of state Ideal Gas law
• Ideal gas equation
• equation of state = formula describing
interconnection between various macroscopically V varies as 1/P, T and n
measurable properties of system.
• For physical states of matter, equation usually PV=nRT where
relates thermodynamic variables of i) pressure, ii) P= Pressure
temperature, iii) volume and iv) number of atoms
to one another. V= volume
T= ⁰K
• For gases, idealized relationship = ideal gas law
n = mole = mass/MW
R =constant = 0.082 Latm/ ⁰Kmol
Dalton’s law of partial pressures Dalton’s law of partial pressures
A mixture of oxygen, hydrogen and nitrogen
• Total pressure of mixture of gases = gases exerts a total pressure of 278
sum of pressures that each would kPa. If the partial pressures of the
exert if it were present alone. oxygen and the hydrogen are 112 kPa
and 101 kPa respectively, what would be
Pt = P1 + P2 + . . . Pn the partial pressure exerted by the
Pt = total pressure of mixture of nitrogen?
gases Ptotal = PO2 + PN2 + PH2
P1, P2, P3, etc. = partial pressures 278 kPa = 112 kPa + 101 kPa + PN2
(same units) of gases in mixture Pnitrogen = 278 kPa - (112 kPa + 101 kPa)
Pnitrogen = 65 kPa
Avogadro’s law
• At constant pressure and temperature, there is Sample problem
a direct relationship between the volume and
number of moles for an ideal gas. A volume of gas equal to 25 L was
• At constant temperature and pressure, volume is collected at 250C and 1.00 atm
directly proportional to the number of moles of pressure. What would be the
gas
volume of the gas if it were
• One mole of a gas at STP (1 atm, 0oC) occupies a
volume of 22.4 L. collected at 1000C and 0.85
• One mole of a gas contains 6.02 x 1023 molecules. atm pressure?
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Sample problem Sample problem
A volume of gas equal to 25 L was collected at A volume of gas equal to 25 L was collected at 250C
250C and 1.00 atm pressure. What would be and 1.00 atm pressure. What would be the volume
of the gas if it were collected at 1000C and 0.85
the volume of the gas if it were collected at
atm pressure?
1000C and 0.85 atm pressure?
Given:
Given: P1 = 1atm T1=25oC = 298o
P1 = 1atm T1= 25oC P2 = 0.85 atm T2=100oC = 373oK
P2 = 0.85 T2=100oC V1 = 25L n = constant
V1 = 25L n= constant
Sample problem Sample problem
Given: Given:
P1 = 1 atm T1= 25oC = 298oK P1 = 1atm T1=25oC = 298oK
P2 = 0.85 atm T2=100oC = 373oK P2 = 0.85 atm T2=100oC = 373oK
V1 = 25L n = constant V1 = 25L n = constant
PV = nRT P1 V1 = nR P2V2
= nR P1 V1 P2V2
= P1 V1 T2 = P2 V2 T1
T1 T2 T1 T2
P1 V1 P2V2 P1 V1 T2 (1atm)(25L)(373o K)
= = nR V2 = = » 36.8L
T1 T2 P2 T1 (0.85atm)(298 o K)
Sample problem
Given:
P1 = 1atm T1 = 25oC = 298oK
P2 = 0.85 T2=100oC = 373oK
V1 = 25L n = constant
P1 V1 T2 Liquids
V2 = (1atm)(25L)(298 o K)
P2 T2 V2 = Fixed volume, variable shape
(0.85atm)(373o K)
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Liquids
• Gases condense into liquids
• Increase- pressure on gas à push molecules Interlude
together àreduce temperature à gas
condenses Intermolecular Forces
• Molecules experience short range and weak (Interparticle forces)
attractive forces (van der Waal’s attractive
forces) van der Waal’s
• Particles far enough from each other à allow
translational motion, slide past each other,
but movement more restricted than gas. 44
Terminologies… IMF = InterMolecular Forces
Warning! (Jim Clark, 2012)
There's a bit of a problem here with modern syllabuses.
The majority of the syllabuses talk as if dipole-dipole
interactions were quite distinct from van der Waals
forces. Such a syllabus will talk about van der Waals
forces (meaning dispersion forces) and, separately,
dipole-dipole interactions.
All intermolecular attractions are known collectively as
van der Waals forces. The various different types
were first explained by different people at different
times. Dispersion forces, for example, were described
by London in 1930; dipole-dipole interactions by
Keesom in 1912.
http://www.chemguide.co.uk/atoms/bonding/vdw.html
Intermolecular forces (of attraction) London dispersion forces
1. London
dispersion • weakest intermolecular force.
forces or • Electrons in constant motion à atom or
induced dipole - molecule can develop temporary
for non-polar (instantaneous and transient) dipole when
molecules (CH4, H2,
CO2) electrons distributed asymmetrically about
2. Dipole-dipole the nucleus.
– Between polar • sometimes called an induced dipole-
molecules (I-Cl, induced dipole attraction.
NH3)
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London dispersion forces London dispersion forces
• temporary attractive force that results when
electrons in two adjacent atoms occupy
positions that make atoms form temporary
dipoles.
• attractive forces that cause nonpolar
substances to condense to liquids and to
freeze into solids when temperature is
lowered sufficiently.
Dipole-dipole Intermolecular forces of attraction
3. H-bonding - H attached to a highly
• attractive forces between positive end of one polar
electronegative atom like F, N, O, Cl, S (H2O, NH3),
molecule and negative end of another polar
in immediate vicinity of another electronegative
molecule.
atom
• much weaker than ionic or covalent bonds and
- special kind of dipole-dipole interaction
have significant effect only when the molecules
involved are close together (touching or almost
touching).
Intermolecular forces of attraction
4. Ion-dipole- ion attracts polar molecule
with opposite partial charge Interlude ends
Intermolecular Forces
(Interparticle forces)
5. Ionic or Electrostatic: Cations and van der Waal’s
anions or electrostatic (NaCl, CaO)
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