Environmental Influence (7) Flashcards

1
Q

What are chemical shifts?

A

The difference in the NMR absorption frequency of protons bound to chemically distinct groups in molecules

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2
Q

How is the frequency of RF absorption influenced by the local chemical environment?

A

differences occur in the absorption frequency of protons bound to chemically different groups in molecules.

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3
Q

What is diamagnetic circulation?

A

term that accounts for spherical charge density and opposes B0

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4
Q

What is the shielding constant?

A

dimensionless, independent of B0, determined by electron density and distribution

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5
Q

How does shielding influence the local magnetic field felt by the nucleus?

A

shielding decreases with increasing electronegativity of adjacent groups

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6
Q

How does the shielding constant affect the Larmor precessional frequency?

A

precess with a slightly smaller Larmor frequency

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7
Q

What is the shielding constant for an isolated hydrogen nucleus?

A

zero

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8
Q

How are shielding and the observed chemical shifts related?

A

Identical 1H nuclei give rise to different absorption positions when in different chemical surroundings, reflected in the chemical shift

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9
Q

How are chemical shifts measured?

A

internal standards report the position of the NMR peaks

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10
Q

Why is frequency not directly measured?

A

its much easier to measure the magnitude of change in field strength

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11
Q

Why is TMS used as the internal standard for proton NMR?

A

all protons are equivalent with a large screening constant

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12
Q

What is δ?

A

NMR chemical shift parameter

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13
Q

How does δ depend on magnetic field strength?

A

it does not; independent

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14
Q

What are the units of δ?

A

ppm

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15
Q

How can δ be defined relative to the spectrometer frequency?

A

(∆v/spectrometer frequency) * e6

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16
Q

How is the area of the observed NMR peak related to the number of magnetically equivalent nuclei?

A

area of the absorption peak is proportional to the number of equivalent nuclei giving
rise to the absorption

17
Q

How are NMR resonance frequencies related to shielding?

A

high shielding = low frequency = upfield
low shielding = high frequency = downfield

18
Q

what does the term upfield refer to in an NMR spectrum?

A

increased δ, high shielding, low frequency

19
Q

what does the term downfield refer to in an NMR spectrum?

A

decreased δ, low shielding, high frequency

20
Q

What is the range of δ for 1H atoms?

A

17.8 x 10^-6

21
Q

What is the range of δ for 13C atoms?

A

260.7 x 10^-6

22
Q

What is the range of δ for 31P atoms?

A

961.1 x 10^-6

23
Q

What is the range of δ for 19F atoms?

A
24
Q

What is the diagmagnetic component of the shielding constant?

A

local induced magnetic field opposes B0, is strongly dependent on the spherical charge density of s electrons near the nucleus

25
Q

How is the diagmagnetic component of shielding dependent on the spherical charge density of the s electrons near the nucleus?

A

strongly

26
Q

How is shielding related to inductive effects?

A

local induced magnetic field opposes the B0 field

27
Q

How is shielding related to electronegativity?

A

shielding decreases with increasing electronegativity of adjacent groups

28
Q

How is shielding related to magnetic anisotropy?

A

shielding of neighboring groups dependent on their location with respect to the bond

29
Q

What are ring currents?

A

secondary fields that act in opposition to the applied field

30
Q

How do ring currents influence the value of σ?

A

includes effects from both shielding and deshielding contributions

31
Q

What is the paramagnetic shielding term?

A

accounts for non-spherical charge density

32
Q

How is the paramagnetic shielding term related to electronic energy levels?

A

inversely proportional