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ch10-3web

ch10-3web

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Chem 5

Chapter 10
The Periodic Table and Some
Atomic Properties
Part 3
November 6, 2002
Wave Function Ψ(x). Ψ(r.θ.φ)
Probability Density Ψ
2
(x). Ψ
2
(r.θ.φ)
Probability 1D Ψ
2
(x)dx. 3D Ψ
2
(r.θ.φ)dV
Screening
Penetration
Effective Nuclear Charge Z
eff
= Z - S
r
n=1
n=2
n=3
n=4
Not fixed orbits, but average r
E= 0
At
∞ = r
Why E
n
negative?
Orbital Energy
2
2
n
Z
R E
eff
H n
− =
Atom or Ion Radius
)
`
¹

+

¹
´
¦
+ =
2
0
2
) 1 (
1
2
1
1
n
l l
Z
a n
r
eff
nl
eff
n
Z
a n
r
0
2

E = E
k
+ V
high V
1
low V
0
y
0
y
1
Potential difference between two points
∆V = V
1
–V
0
= mg y
1
- mg y
0
= F ∆y
Potential energy
Need a reference point!
Total Energy
Unbound and escaping
“Pathfinder” E> 0
For a bound satellite
with fixed orbit E< 0
0
2m
p
2
v
E
2 2
k
≥ = =
m
V
r
Define V=0 at
r
mM
r V − ∝ ) (
∞ → r
Potential Energy
r is the center to center distance
of the object and the earth, with
masses m and M respectively.
2
r
mM
dr
dV
F ∝ =
0
V = mg y
Gravitational Potential
r
e Ze
r V

− = ) (
Potential Energy
Fixed Bohr orbits
Probability distributions of r
according to Schrödinger Eq.
E = E
k
+ V
E < 0 Bound
E > 0 Unbound, like “Pathfinder”
0
2
1
< = + = V V E E
k n
2
2
n
Z
R E
H n
− =
Total orbital energy is quantized
For bound states
V
∞ → r
Define V=0 at
r
Columbic Potential
Zero Point Energy and Uncertainty Principle
The kinetic energy is E
k
= <p
2
>/2m, p being the momentum of
the electron.
∆x
Probability
Density for x
P(x)
x
Probability
Density for p
P(p)
p
0
∆p
Uncertainty Principle
E
k
= <p
2
>/2m >0
For the minimum E
k
, <p>= 0
∆x ∆p >= h/4π
This is the minimum kinetic energy
- Zero Point Energy
∆p = h/(4π∆x)
r
e Ze
r V

− = ) (
Potential Energy
V
∞ → r
Define V=0 at
r
With the Zero Point Energy,
E
k
>0 even for the lowest E.
The electron is not at rest at
the nucleus.
We could estimate the Bohr
radius based on the
Uncertainty Principle
(Lecture notes 10-1).
Columbic Potential
Ionization Energy
Na(g) →Na
+
(g) + e
-
I
1
=496kJ/mol
More generally, I.E. is the minimum energy needed to
remove an electron from the nth shell in a gaseous atom.
2
2
2
2
2
2
n
Z
R
Z
n
Z
R E E E I
eff
H
eff eff
H i f
=
|
|
.
|

\
|

− = − = ∆ =
n
E I =
2
2
n
Z
R I
eff
H
=
Alkali metals low I.E.
Noble gases high I.E.
Periodic trends
Increasing across period
Decreasing down group
Z
eff
n=3
n=2
n=2
Z
eff
n=3
n=4
Trends in First IE
I
o
n
i
z
a
t
i
o
n

E
n
e
r
g
y
Ionization Energy
Larger Z
eff
Arrow - Increasing
Larger n
2
2
n
Z
R I
eff
H
=
How to measure I.E.? Photoelectron Spectroscopy
p470
Ne
Kinetic Energy
analyzer
Kinetic energy of the free electron (like the Pathfinder)
Continuum
hv E
k
I.E.
- Photoelectric effect applied not to
metals but to free atoms
I.E. = - E
n
= hv – E
k
Orbital Energies Measured by Photoelectron Spectroscopy
2
2
,
n
Z
R E
eff
H l n
− =
Experimental
Measurement of Z
eff
Electron Affinity
The energy change associated with the addition
of an electron to a gaseous atom.
Cl(g) + e

→Cl

(g)
Exothermic ∆E= -349 kJmol
-1
EA = ∆E
the electron affinity is negative if ∆E<0.
Two definitions!
the electron affinity is positive if ∆E<0.
EA = -∆E
We use the first one.
-200
-100
0
100
200
300
400
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19
ATOMIC NUMBER
-
E
L
E
C
T
R
O
N

A
F
F
I
N
I
T
Y
H
He
Li
Be
B
C
N
O
F
Ne
Na
Mg
Al
Si
P
S
Cl
Ar
Electron Affinities
Larger
Z
eff
2
2
n
Z
R E
eff
H
− =
Cl + eÆCl
-
n from 3 to 4
Z
eff
~0
More repulsion
than attraction
Tends to be more exothermic across period
Trends in Electron Affinities
More negative
Electron Affinity
E
l
e
c
t
r
o
n

A
f
f
i
n
i
t
y
M
o
r
e

n
e
g
a
t
i
v
e
2
2
n
Z
R E
eff
H
− =
Arrow - Increasing
Cations are smaller than their corresponding
neutral atoms.
One less electron pulled in by nuclear charge
n=3
n=2
Smaller Z
eff
Larger Z
eff
eff
n
Z
n
r
2

Anions are larger than their corresponding neutral
atoms.
Same Z and repulsion among electrons increases radius
Z
eff
is smaller for an anion.
eff
n
Z
n
r
2

The more negative charges, the bigger the ion
) (O r < ) (O r < (O) r
– 2 -
I
n
c
r
e
a
s
i
n
g

A
t
o
m
i
c

R
a
d
i
u
s
I
n
c
r
e
a
s
i
n
g

I
o
n
i
c

R
a
d
i
u
s
n
Z
eff
eff
n
Z
n
r
2

Increasing Atomic Radius
Increasing Ionic Radius
Is photoexcitation the only way to generate cations?
Of course not!
Where is the energy coming from?
Demo: The reaction of Na and Cl
) ( 2 ) ( ) ( 2
2
s NaCl g Cl s Na ÷→ ÷ +
Ionization
Energy of Na
Electron
Affinity of Cl
Columbic
Attraction

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