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Lecture

The document discusses the physical properties of bond lengths, bond strengths, and acidity in organic molecules. It outlines how bond lengths are influenced by atomic size, bond order, and hybridization, while bond strengths are related to bond dissociation energies and molecular structure. Additionally, it provides pKa values for various functional groups, illustrating trends in acidity based on electronegativity and molecular charge.

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5 views2 pages

Lecture

The document discusses the physical properties of bond lengths, bond strengths, and acidity in organic molecules. It outlines how bond lengths are influenced by atomic size, bond order, and hybridization, while bond strengths are related to bond dissociation energies and molecular structure. Additionally, it provides pKa values for various functional groups, illustrating trends in acidity based on electronegativity and molecular charge.

Uploaded by

chachasilvester15
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© All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Handout #3, 5.

12 Spring 2003, 2/12/03


Physical Properties: Bond Length, Bond Strength & Acidity

A. Bond Lengths: mostly dependent on atomic size, bond order, and hybridization

Bond Lengths (Å)


• Multiple Bonding: Bond
3 3 3 3 length depends strongly on
sp –sp C C 1.54 sp –sp C O 1.42
bond order (length: single >
sp2–sp2 C C 1.34 sp2–sp2 C O 1.22 double > triple)
sp–sp C C 1.20

Bond Lengths (Å)

sp3 C H 1.09 sp3–sp3 C C 1.54 • Effect of hybridization on


length of single bonds: C–H
sp2 C H 1.086 sp3–sp2 C C 1.50 and C–C bonds shorten slightly
sp C H 1.06 sp3–sp C C 1.47 with increased s character on
carbon

B. Bond Strengths/Bond Dissociation Energies (BDEs): Energy for homolytic bond


cleavage to uncharged radical fragments

X X X. X.

• Bond strengths are bond


energies for a certain bond
averaged over many different
Common Bond Strengths (kcal/mol) molecules.
• Bond dissociation energies are
C C 81 C O 79 for a particular molecule and are
dependent on the specific
molecular structure (Bond
C C 145 C O 173 Strength ± 20 kcal/mol)
• Multiple Bonding: Bond
C C 198 C H 98 strength depends strongly on
bond order (strength: single <
double < triple)

Data taken from: Advanced Organic Chemistry, 3rd Edition, F. A. Carey and R. J. Sundberg
C. Acidity of Organic Molecules

Functional Group Acid Approximate pKaValues Conjugate Base


(in water) increasing
basicity

alkane-sp3 H–CH3 48 –
CH3

alkene-sp2 H–CH=CH2 44 –
CH=CH2
–
amine H–NH2 38 NH2
–
hydrogen H–H 35 H
–
alkyne-sp H–C≡CH 25 C≡CH
–
alcohol H–OCR3 17 OCR3
–
water H–OH 15.7 OH
–
thiol H–SR 10–11 SR

ammonium H–+NR3 10–11 NR3


–
nitrile (cyanide) H–C≡N 9.2 C≡N
–
phenol H–OAr 8–11 OAr
–
carboxylic acid H–OC(O)R 4–5 OC(O)R
–
H–F 3.17 F

hydronium H–+OH2 –1.74 OH2


–
H–Cl –7 Cl
–
H–I –10 I

increasing
acidity

• Acidity increases across a row: H–C < H–N < H–O < H–F (electronegativity)
• Acidity increases down a period: H–F < H–Cl < H–Br < H–I (size)
• Neutral species less acidic than corresponding positively charged species: H–OH < H–+OH2
pKa data from: Advanced Organic Chemisry, 4th Ed., J. March

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