TRENDS IN ATOMIC PROPERTIES

AFFINITY FOR ELECTRONS subtitle Click to edit Master AND ELCTRON AFFINITY

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ARCIAGA, CRUZ, DELA CRUZ, PLUMO, ROXAS CHEM 120 - B

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introduction

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IN BUILDING UP THE PERIODIC TABLE BY STARTING WITH THE HYDROGEN ATOM AND SUCCESSIVELY ADDING A PROTON TO THE NUCLEUS AND AN ELECTRON TO THE EXTRANUCLEAR SHELL (this process is called the Aufbau Principle), WE MUST ALLOW FOR THE SCREENING EFFECTS. IN OTHER WORDS, WE MUST ACCOUNT FOR THE FACT THAT ORBITALS OF THE SAME n QUANTUM NUMBER BUT DIFFERENT l QUANTUM NUMBER MAY HAVE DIFFERENT ENERGIES IN A GIVEN ATOM. THE ONLY ad hoc ASSUMPTION WE NEED INTRODUCE AT THIS POINT IS THAT OF THE Pauli Exclusion Principle, WHICH PERMITS ONLY TWO ELECTRONS TO OCCUPY THE SAME SPATIAL ORBITAL OR TO HAVE THE SAME SPATIAL WAVE FUNCTION.
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IN A POLYELECTRONIC ATOM, THE NUCLEAR POSITIVE CHARGE EXPERIENCED BY AN ELECTRON WILL BE Z (NUCLEAR CHARGE) WHEN r = 0 AND WILL DECREASE TOWARD UNITY AS r APPROACHES INFINITY . THE DECREASE IN THE EFFECTIVE NUCLEAR CHARGE (Z*) WITH INCREASING r IS A CONSEQUENCE OF THE SHIELDING OF NUCLEAR CHARGE BY THE OTHER ELECTRONS TO THE NUCLEUS.

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PAULI EXCLUSION PRINCIPLE

THE PHYSICAL PHENOMENON ON WHICH THE Pauli Principle IS BASED IS THAT TWO PARTICLES WITH THE SAME SPIN DO A BETTER JOB OF AVOIDING EACH OTHER IN SPACE THAN DO TWO ELECTRONS OF OPPOSITE SPIN QUANTUM NUMBER.

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SPIN CORRELATION OF ELECTRON MOTIONS

THE CHEMICAL SIGNIFICANCE OF THIS CORRELATION IS THAT, SINCE ELECTRONS ARE CHARGED AND REPEL ONE ANOTHER, THE REPULSION IS LESS, BY AN AMOUNT CALLED THE EXCHANGE ENERGY, FOR ELECTRONS OF LIKE SPIN THAN FOR ELECTRONS OF DIFFERENT SPIN.

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CHARGE CORRELATION ENERGY

THIS DICTATES THAT A LOWER ENERGY SITUATION EXISTS IF THE TWO p ELECTRONS HAVE DIFFERENT ANGULAR FUNCTIONS. SPIN CORRELATION FURTHER AFFORDS A LOWER (MORE NEGATIVE) ENERGY FOR LIKE SPINS.

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SPIN CORRELATION AND ITS EXCHANGE ENERGY ARE THE PHYSICAL BASIS FOR THE OFTEN CITED STABILITY OF THE HAF-FILLED SHELL. IT IS SIMPLY A MATTER OF CHOOSING THE ELECTRON ARRANGEMENT THAT LEADS TO THE LOWEST ELECTRON-ELECTRON REPULSIONS. OBVIOUSLY, PLACING TWO ELECTRONS IN THE SAME ORBITAL WILL LEAD TO HIGHER REPULSIONS THAN IF THEY MOVE IN DIFFERENT SPATIAL ORBITALS (THE ELECTRONS HAVE THE SAME CHARGE).

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IN ADDITION TO THE LOWER ENERGY MADE POSSIBLE BY ALLOWING SEPARATE ORBITAL MOTIONS FOR THE TWO CHARGED PARTICLES, THE SPIN CORRELATION ALLOWS FOR A FURTHER REDUCTION IN REPULSION IF BOTH HAVE THE SAME SPIN.

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TRENDS IN THE ELECTRON AFINITY

INFLUENCE ON THE ELECTRONIC Click to edit Master subtitle CONFIGURATION AND ENERGY OF AN style DICTATED BY FINE DETAILS OF ATOM ELECTRON REPULSIONS

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AND AFFINITY FOR THE TENDENCY ELECTRON OF AN ATOM (OR ION) S TO ATTRACT ADDITIONAL

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ELECTRON IS CALLED AFFINITY FOR ELECTRONS. IT IS MEASURED BY A THERMODYNAMI C QUANTITY CALLED Electron Affinity. ELECTRON AFFINITY IS

THE TREND OF INCREASING AFFINITY FOR ELECTRON IS OPPOSITE THE ALGEBRAIC INCREASE IN THE ELECTRON AFFINITY VALUES: THE GREATER THE AFFINITY FOR ELECTRONS, THE MORE NEGATIVE THE VALUE OF ELECTRON AFFINITY IS. REPRESENTATIVE ELECTRON AFFINITY

ELEMENTS H Li Na K Rb

(kJ/mol) -77 -58 -53 -48 -47

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ALTHOUGH THERE ARE SOME EXCEPTIONS, GENERALLY, AFFINITY FOR ELECTRON INCREASES FROM LEFT TO RIGHT ACOSS A PERIOD, THAT IS, ELECTRON AFFINITY VALUES BECOME MORE NEGATIVE, BUT ONLY UP TO 3/13/13 17. GROUP

THE ELECTRON CONFIGURATION AND ENERGY OF AN ATOM ARE DICTATED BY FINE DETAILS OF ELECTRON REPULSIONS. A GOOD ILLUSTRATION CAN BE FOUND IN THE TRENDS IN IONIZATION POTENTIAL AND

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THE VALENCE CONFIGURATIONS OF THESE ELEMENTS ARE ns2npx, WHERE x PROGRESSES FROM 1 THROUGH 6. THE TREND OF INCREASING ELECTRON AFFINITY ACROSS THIS SERIES IS BROKEN AT THE CONFIGURATION s2p4. THAT IS, THE CONFIGURATIONS WITH x = 1, 2, 3 FOLLOW A SMOOTHLY INCREASING TREND, AS DO THE CONFIGURATIONS WITH x = 4, 5, 6. THE LATTER SERIES IS SIMPLY SHIFTED TO LOWER ELECTRON AFFINITY FROM THE VALUES THAT WOULD BE EXTRAPOLATED FROM x = 1, 2, 3.

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ELECTRON AFFINITY TRENDS EXPLAINED

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Electron affinities generally become smaller as we go down a column of the periodic table for two reasons: The electron being added to the atom is placed in larger orbitals, where it spends less time near the nucleus of the atom. The number of electrons on an atom increases as we go down a column, so the force of repulsion between the electron being added and the electrons already present on a neutral atom becomes larger.

1.

2.

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NOBLE GASES AND THE HALOGENS

The electron affinity of the noble gases is sometimes taken to be as negligible since these gases already have a stable electronic configuration and their orbitals are fullyfilled.

Electron affinity for the halogens is relatively high since the process for an atom to accept an electron to fill out a shell and therefore attain an inert gas electron configuration is energetically favorable.

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NITROGEN

WHY IS ELECTRON AFFINITY POOR FOR NITROGEN?

Electron affinity for nitrogen is poor since the value for electron affinity will be unstable, meaning EA > 0. It is unstable since the electron which is accepted by the gaseous nitrogen must go into an occupied orbital, therefore there will be repulsion and is repulsion results to unstable EA.

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OXYGEN

HOW ABOUT OXYGEN?

The first EA for oxygen does not result to unstable one even if the added electron must go into an occupied orbital. This is due to the large effective nuclear charge of oxygen that can overcome the repulsion between the electrons.

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REFERENCES

PURCELL. 1980. An Introduction to Inorganic Chemistry. ZUMDAHL. Chemistry. 5th ed.

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THANK YOU!
Click to edit Master subtitle ARCIAGA style
CRUZ DELA CRUZ PLUMO ROXAS

CHEM 120 B (Electron Affinity) 3/13/13

Some things to think about

In Slide #11, is the process given at the bottom really the process to which we attribute electron affinity? Why can electron affinity be either positive or negative? Na has a negative EA! Why dont we see compounds where Na is the anion? What can our lessons on spin and charge correlation add to our understanding of the trends and other observed values for electron affinity?

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