UNIVERSITY OF VICTORIA FINAL EXAMINATION ...web.uvic.ca/~chem213/213Fin-06.pdfCHEM 213 2006 Final Exam Page 6 Compound B, the smelly component emitted by pulp mills, showed M+ at m/z

UNIVERSITY OF VICTORIA

FINAL EXAMINATION, DECEMBER 2006

CHEMISTRY 213 - F01

PRACTICAL SPECTROSCOPY

TIME: 3 HOURS

INSTRUCTOR: Dr Reg Mitchell

IN THIS EXAM THERE SHOULD BE 26 PAGES (check this)

(includes THIS COVER SHEET) + A BLUE SIGNATURE SHEET

[NOTE PAGES ARE PRINTED BOTH SIDES]

YOU ALSO SHOULD HAVE

A GREEN COMPUTER SHEET

A YELLOW ANSWER SHEET PACK (2 sheets, 4 sides)

A PINK DATA SHEET PACK (3 sheets, 6 sides)

Report to the invigilator if any of these are missing now

ANSWER QUESTIONS 1-54 [1.5 marks each] ON THE GREEN COMPUTER SHEET

WITH A PENCIL = 81 marks;

ANSWERS THAT REQUIRE YOU TO DRAW A STRUCTURE, GIVE A FORMULA,

ETC, HAVE LETTERS AS QUESTION #’S. ANSWER THESE ON THE YELLOW

SHEETS PROVIDED. USE A PEN OR PENCIL, BUT MAKE SURE YOUR ANSWER IS

READABLE = 80 marks. Total Marks = 161; Total minutes = 180!

MAKE SURE YOUR NAME (LAST(FAMILY) NAME FIRST) AND REGISTRATION

NUMBER ARE ON BOTH THE GREEN COMPUTER SHEET AND THE YELLOW

ANSWER SHEETS - DO THIS NOW, AND ALSO SIGN THE BLUE SHEET

PLACE YOUR STUDENT ID ON THE TOP RIGHT CORNER OF THE TABLE

ELECTRONIC CALCULATORS ARE PERMITTED, BUT MUST NOT CONTAIN

STORED PROGRAMS OR FORMULAE

CHEM 213 2006 Final Exam Page 2

NUMBERED QUESTIONS: ANSWER ON THE GREEN COMPUTER SHEETPROVIDED USING A PENCIL; CHOICES MAY BE USED MORE THAN ONCE.SOME QUESTIONS MAY REQUIRE DATA SUPPLIED ON THE PINK SHEETS!

Four IR spectra (Q1-4) and ten compounds (a - j) are shown below. Assign each spectrumto a compound.

Q1

Q2

Q3

Q4

| | | | | | | | | | 34 30 26 22 18 17 16 9 8 7 00's cm-1


Compounds a - j for Q 1-4

CO2Et

COOH OCCH

C N

CHO

COCl

NHCH3CH3

NH2 CHO

(a) (b) (c) (d) (e)

(f) (g) (h) (i) (j)

Compound A, which is aromatic, shows the following ir spectrum

Scale | | | | | | 1700 1220 1050 860 770 690 cm-1

In its mass spectrum, A showed an M+ at 142 and an M+2 peak at 144 in a 3:1 ratio. Aswell an 8% (M+1) peak at 143 was seen. High resolution MS indicated only one oxygenatom to be present in a molecule of A. Fragment peaks were seen at m/z 15, 31 and 35.

5 How many carbon atoms are present in a molecule of A(a) 3 (b) 4 (c) 5 (d) 6 (e) 7 (f) 8 (g) 9 (h) 10 (i) 11 (j) 12

Determine the molecular formula for A and write it on the yellow answer sheet [2 marks]

Determine the structure of A and draw it on the yellow answer sheet -show all H’s [5marks]


O

OH

TestosteroneHO

OH

Estradiol

The structures of the principal male and female sex hormones, testosterone and estradiolare shown above.Using the wavelength choices (nm) (a) 315-325 (b) 270-280 (c) 250-260 (d) 210-215 (e) 200-205 (f) 180-190and ε choices (a) 10,000 (b) 1000 (c) 100 (d) 30 (e) 1

6 Where would you expect to find n 6 π2* for testosterone7 What ε value would this (Q#6) absorption have8 Where would you expect to find π2 6 π2* for testosterone9 What ε value would this (Q#8) absorption have10 Where would you expect to find the longest wavelength absorption for estradiol11 Assuming you had access to any uv-vis spectrometer, where would the most intense

absorption for estradiol appear

Using the choices(a) hypsochromic shift (b) bathochromic shift (c) no shift

12 How would you expect the spectrum of estradiol to change on addition of NaOH


Tricarbonylchromiumbenzene, C6H6Cr(CO)3 forms intense orange crystals.13 At what wavelength (nm) is this compound absorbing light:(a) 670 (b) 600 (c) 550 (d) 500 (e) 450 (f) 400(g) 350 (h) 300 (i) 250 (j) 180

then using the transition choices:(a) π9 6 π9* (b) π1 6 π9* (c) π9 6 n* (d) n 6 π9* (e) L 6 M CT(f) M 6 L CT (g) d 6 d (h) π9 6d (i) d 6 π9* (j) π1 6 d*and ε choices: (a) 3000 (b) 300 (c) 30

14 What transition produces this absorption15 What would its ε value be16 When this compound is oxidized by air, a pale green chromium compound is

formed. What transition is giving this pale green color17 What would its ε value be

18 How large will the M+1 ion be in the mass spectrum oftricarbonylchromiumbenzene [Chromium’s lowest mass isotope = 50, and 51Cr haszero abundance]

(a) 29% (b) 100% (c) 1% (d) 6% (e) 67% (f) 10% (g) 4% (h) 82% (i) 24% (j) 0%


Compound B, the smelly component emitted by pulp mills, showed M+ at m/z 62 and alsopeaks at 63 and 64 in a 100:2.2:4.4 ratio. Fragment peaks were seen at m/z 15, 32 and 47.

The 1H NMR spectrum of compound B consisted of only a single peak.

[Isotopic data is available on the pink sheets]

Determine the structure of compound B and write in the space provided on the yellowanswer sheet. [3 marks]

19 What would you see in the 13C NMR spectrum (not decoupled) of compound B [nospin active nuclei is present other than those you are familiar with](a) s (b) d (c) t (d) q (e) 5 (f) 6 (g) 7 (h) dq (i) d7 (j) tq

20 What would be the approximate J value (Hz) in this spectrum(a) not coupled (b) 0 (c) 1 (d) 5 (e) 15 (f) 50 (g) 200 (h) 1000 (i) 10000


A product C was obtained from a reaction.The COSY and NOESY spectra of the product, compound C, are shown on the next page.Chemical shifts are approximate. Start by assigning the obvious chemical shifts, and then consider which hydrogens are coupled to these, and then which interact through space.Then choose one of the following 8 isomers of C as its structure and enter its number on theyellow answer sheet [8 marks]Answer choices:

CHOH

CH3

H

Cl CH3D D

Cl

Cl H

H

CHOH

H

CH3

Cl CH3D D

Cl

Cl H

H

CHOCH3

H

H

Cl CH3D D

Cl

Cl H

H

CHOH

CH3

H

CH3 ClD D

Cl

Cl H

H

CHOCH3

H

H

CH3 ClD D

Cl

Cl H

H

HH

CH3

CHO

Cl CH3D D

Cl

Cl H

H

HCHO

CH3

H

Cl CH3D D

Cl

Cl H

H

HH

CH3

CHO

CH3 ClD D

Cl

Cl H

H

1 2

3 4

5 6

78


NOESY SPECTRUM OF C (approx chem shifts given)(note COSY correlations have been removed, and each peak is shown as a line)

#H’s 1 1 1 1 1 3 3approx δ 10 5 3 2 1

(scale distorted)


COSY SPECTRUM OF C

#H’s 1 1 1 1 1 3 3 approx δ 10 5 3 2 1(scale distorted)

Do not forget to put your answer on the yellow sheet!


For the compound F

OCH3

Hb

HHa

CH3O

Use the choices of chemical shift(a) 8.16 (b) 7.70 (c) 7.37 (d) 7.27 (e) 7.24(f) 7.04 (g) 6.84 (h) 6.56 (i) 6.38 (j) 6.33

21 Calculate the chemical shift for Ha

22 Calculate the chemical shift for Hb

Using the choices:(a) ABCD (b) ABCX (c) ABC (d) AA’B (e) A2B(f) A2X (g) AA’X (h) A3 (i) AA’MX (j) A2MX

23 What will be the spin system for the aromatic protons at 60 MHz24 What will be the spin system for the aromatic protons at 600 MHz


For the molecule phosphoric acid, PO(OH)3 [often written as H3PO4; P is in group 5 (or 15)]

25 At what frequency (Hz) would you expect to find the O-H stretch(a) 4.7 x 108 (b) 5 x 108 (c) 5.3 x 108 (d) 5.3 x 109 (e) 4.7 x 1011

(f) 1 x 1014 (g) 7.5 x 1014 (h) 1 x 1015 (i) 7 x 1015 (j) 3 x 1018

Using:(a) 0 (b) 1 (c) 2 (d) 3 (e) 4 (f) 7 (g) 17 (h) 18 (i) 21 (j) 24

26 How many ir inactive O-H stretches would you expect to see27 How many fundamental vibrations are possible

and using (cm-1) :(a) 2200 (b) 1720 (c) 1680 (d) 1300 (e) 800 (f) 200

28 Where would you expect to see the O=P stretch

Then using(a) s (b) d (c) t (d) q (e) ddd (f) dt (g) dq (h) 5 lines (i) 6 lines (j) 7 lines

29 How will the 31P NMR (see data sheet) spectrum appear at low temperature30 How will the 1H NMR spectrum appear at room temperature31 How will the 1H NMR spectrum appear at low temperature

Some profs use a red laser pointer during lectures. 32 What is the energy (kJ mole-1 ) of a mole of “laser photons”(a) 240 (b) 175 (c) 200 (d) 365 (e) 402 (f) 498(g) 1.75 (h) 2.4 (i) 0.365 (j) 0.05


The transition from v=0, J=3 to v=1, J=2 of one of the fundamental vibrations of CO2 in itsir spectrum is found at 2338 cm-1, while the transition from v=0, J=1 to v=1, J=2 is found at2358 cm-1

33 What is the rotational spacing constant B (cm-1)(a) 0.5 (b) 1.0 (c) 1.5 (d) 2.0 (e) 2.5(f) 3.0 (g) 4.0 (h) 5.0 (i) 8.0 (j) 16

34 What is the fundamental frequency (cm-1) of this vibration(a) 2350 (b) 2352 (c) 2354 (d) 2356 (e) 2360(f) 2348 (g) 2346 (h) 2342 (i) 2338 (j) 2336

35 Where would the first hotline be found (cm-1)(a) 4668 (b) 4704 (c) 2338 (d) 2372 (e) 1160 (f) 1190

36 What is the energy for the v=1, J=0 level for this vibration (kJ mole-1)(a) 0.14 (b) 0.28 (c) 4.2 (d) 14 (e) 28(f) 42 (g) 55 (h) 56 (i) 68 (j) 70

37 In nature, CO2 exists as 12CO2, 13CO2 and 14CO2. What will be the order for ν0.(a) 12C < 13C < 14C (b) 13C < 14C < 12C (c) 14C < 13C < 12C (d) 14C < 12C < 13C(e) 12C < 14C < 13C (f) 13C < 12C < 14C

38 The vibration in Q#34 will show (branches)(a) P,Q,R (b) P,R (c) Q (d) P (e) R(f) P, Q (g) Q, R


39 If the spin quantum number for D is 1, how will the 13C NMR spectrum of DCCl3 appear

(a) 1:2:1 triplet (b) 1:1:1 triplet (c) 1:3:3:1 quartet (d) 1:1:1:1 quartet(e) 1:4:1 triplet (f) 1:1 doublet (g) 1:3:1 triplet (h) 3:1 doublet(i) 1:3 doublet (j) singlet

40 At UVIC, we use the 360MHz proton magnet to observe deuterium spectra. Whatfrequency (MHz) will the probe operate at to observe 2D (pink data sheet)

(a) 300 (b) 120 (c) 100 (d) 278 (e) 66.7(f) 1080 (g) 53 (h) 27 (i) 11 (j) 9


For the molecule D:

Y

OCH3

CH3O CH2 ClPt

Cl H

89Y has a spin of 1/2 and is 100% abundant.Assume 1JPt,H = 600 Hz, 2JPt,Y = 100 Hz, 2JPt,H = 60 Hz, 2JY,H = 50 Hz, 3JY,H = 15 Hz,4JPt,H = 3 Hz and all 5JX,Z are zero. Assume normal H-H couplings.

using:(a) t8 (b) 8 (c) dt (d) q (e) td7 (f) dt8 (g) dtd7 (h) dtq (i)ddt (j) tq

41 How will the 195Pt spectrum appear42 How will the 1H spectrum of the Pt-H appear for a molecule that does not contain

195Pt

43 How will the 1H spectrum of the Pt-H appear for a molecule that only contains 195Pt44 How will the 89Y spectrum appear for a molecule that does not contain 195Pt45 How will the 89Y spectrum appear for a molecule that only contains 195Pt

46 What will be the width (Hz) of the 195Pt spectrum (i.e. distance in Hz between far lefthand and far right hand lines)

(a) 2118 (b) 820 (c) 1280 (d) 2460 (e) 920(f) 960 (g) 1059 (h) 1080 (i) 609 (j) 618


47 For the compound F3C-PtHCl2, if 1JPt,H = 600 Hz, 2JPt,F =100Hz and 3JH,F = 16 Hz,and if the proton spectrum shows the most upfield line is 2324 Hz shielded fromTMS, what is the chemical shift of this H. The spectrum was run at 400 MHz

(a) -5.00 (b) -4.00 (c) +5.00 (d) +4.00 (e) -5.81(f) +5.81 (g) -4.20 (h) +4.20 (i) -5.20 (j) +5.20

48 How many Hz separate the tallest peaks in the natural abundance proton spectrumof this compound

(a) 8 (b) 16 (c) 32 (d) 48 (e) 50 (f) 100 (g) 300 (h) 600

49 What is the spin system of this compound with a spin active platinum(a) AB3X (b) ABB’B”X (c) AM3X (d)AMM’M”X(e) AX3 (f) AXX’X” (g)ABCMX

For the fluorines of the compound referred to in Q47, what would be the intensities of thelines in the real fluorine spectrum of an actual natural abundance sample - write youranswer using the format 1:1:2:1etc on the yellow answer sheet [3 marks]

50 If one had a spectrometer which could measure 13C, 19F, 195Pt and 1H on the sameprobe using the same magnetic field strength, in which order would the nucleiappear to resonate as the frequency of the probe was increased

(a) Pt<C<F<H (b) H<F<C<Pt (c) C<Pt<H<F (d) F<H<Pt<C(e) Pt<F<H<C (f) C<H<F<Pt (g) H<F<Pt<C (h) F<Pt<C<H

THE OBJECTIVE IN THE FOLLOWING QUESTIONS IS TO SOLVE THE


STRUCTURES. THERE ARE SOME QUESTIONS TO ANSWER ON THE GREENCOMPUTER SHEETS; YOU WILL DRAW YOUR SOLUTION TO EACHSTRUCTURE ON THE YELLOW SHEETS. WORK SPACE IS PROVIDED AFTER EACHQUESTION, THIS WILL NOT BE MARKED; ONLY GIVE YOUR FINAL ANSWER ONTHE YELLOW SHEETS, giving more than one answer leads to penalties.

ALL Proton spectra are 300 MHz

COMPOUND E, C4H5BrO2

51 How many DBE has compound E(a) 0 (b) 0.5 (c) 1 (d) 1.5 (e) 2 (f) 2.5 (g) 3 (h) 3.5 (i) 4 (j) 4.5

The IR spectrum:

| | | 3400 2400 1690 cm-1

52 What functional group is present in compound E(a) alcohol (b) aldehyde (c) acid (d) 10 amine (e) 20 amine(f) ester (g) ketone (h) ether (i) aldehyde (j) acid bromide

13C NMR:170s 137s 131t 39t


1H NMR Spectrum

The peak at δ 7.27 is solvent

Write your proton integration values on the yellow answer sheet in the place providedin the form a:b:c:d [2 marks]

Draw your structure for compound E on the yellow answer sheet in the place provided [8 marks]


Compound F, C9H9Br

53 How many DBE has compound F(a) 0 (b) 1 (c) 2 (d) 3 (e) 4 (f) 5 (g) 6 (h) 7 (i) 8 (j) 9

IR:

13C NMR spectrum: 136s 134d 129d 128d 127d 126d 36t

1H NMR Spectrum [300MHz]

Integrations 5 : 1 : 1 : 2Multiplicity m d dt d * = overlapping dt

Draw your structure for compound F on the yellow answer sheet in the place provided[8 marks]


Compound G, C4H11O3PPhosphorus is pentavalent in this compound.

13C NMR Spectrum: 62td 16qd

13C{31P} NMR Spectrum: 62t 16q

IR Spectrum:

| | | 2400 ~1300 ~1000 cm-1

Ignore the small bands at 3400 cm-1, and (for now) the band at 2400 cm-1.Consider what the oxygens must be.

1H NMR Spectrum [300MHz]:

<----------------------->Integrations: 1 : 4 : 6

Multiplicity d ~qd t


Draw your structure for compound G on the yellow answer sheet in the place provided[10 marks]

Also draw on the yellow answer sheet in the place provided, the vibration you think isresponsible for the 2400cm-1 peak in the IR spectrum [1 mark]


COMPOUND H, C10H14O

54 How many DBE are present in compound H(a) 0 (b) 1 (c) 2 (d) 3 (e) 4 (f) 5 (g) 6 (h) 7 (i) 8 (j) 9

The IR spectrum :

| 3400 cm-1

The 13C NMR spectrum:152s 137s 131s 126d 122d 116d 27d 23q 19q

The 1H NMR spectrum [300MHz]:

Integrations: 1 :1:1 : 1 : 1: : 3 : 6Multiplicities d d s s 7 s dThe peak at δ 4.8 exchanges with D2O. Only the * 6.5 singlet is significantly shielded.


From the above data, you should be able to get two isomers as possible structures.Draw both of these isomers now on the yellow answer sheet. [12 marks]. When you have finished the exam, come back and using the data below, refine your answerto a single isomer which you should then circle [5 marks].

An HMQC (J=135 Hz) [Short range Hetcor] spectrum of compound H d d s s 7 s d


Part of the HMQC (J=10 Hz) [Longe range Hetcor] spectrum of compound H δ 4.8 3.2 2.2 1.2

Now circle the correct isomer for compound H on the yellow answer sheet in the spaceprovided. [ 5 marks]


COMPOUND I gave a high resolution mass spectrum molecular weight of 181.073, whichindicated one of the following formulaeC H N O6 13 - 67 9 4 29 11 1 312 9 2 -

Determine the molecular formula for compound I and enter it on the yellow answer sheetin the space provided. [1 mark]

The IR spectrum of compound I:

The IR indicates a nitro group (-NO2) is present. The 13C NMR spectrum of I:161s 144s 133s 127s 124d 107d 56q 26q 22q

The proton spectrum of I:

Integrations 1 : 1 : 3 : 3 : 3


Using the observed chemical shifts, you should be able to determine a structure forcompound I.You can confirm it with the HMQC spectra below:

HMQC (J=135) [Short range Hetcor]

Protons

carbons

Part of the HMQC (J=10) [Longe range Hetcor]

Protons

carbons

Determine the structure of compound I and draw it on the yellow answer sheet[12 marks]


-END-

FINAL EXAMINATION, DECEMBER 2006 YELLOW ANSWER SHEETS

CHEMISTRY 213 - F01 PRACTICAL SPECTROSCOPY

LAST NAME:

FIRST NAME AND INITIAL:

REGISTRATION NUMBER:

ALSO PUT YOUR NAME ON SHEET TWO (Side 3).

GIVE ONLY YOUR FINAL STRUCTURES ON THIS SHEET, SPACE FOR ROUGH

WORK IS PROVIDED ON THE QUESTION SHEET. Part marks will be given for partial

structures or partly correct structures; do NOT give ANY of the detail as to how you

derived the structure. THESE PAGES ARE PRINTED BOTH SIDES!

MAKE SURE YOU SHOW ALL ATOMS INCLUDING HYDROGENS

IN YOUR FINAL STRUCTURES

MARKS FROM THIS SHEET [/80] =

{Page 3} FORMULA FOR COMPOUND A [2 MARKS] =

{Page 3} STRUCTURE FOR COMPOUND A [ 5 MARKS]

{Page 6} STRUCTURE FOR COMPOUND B [3 marks] =

{Page 7} STRUCTURE FOR COMPOUND C [8 marks] =

[a number from 1-8 is required]

{Page 15} Relative intensities of the fluorine lines for compound of question 47 [3 marks] =

[format required = 1:b:c: etc] =

{Page 17} COMPOUND E: Proton Integration values [a:b:c: d][2 marks]=

{Page 17} STRUCTURE FOR COMPOUND E (show all H’s) [8 marks]

Yellow Answer Sheet 2, page 3 213 Final 2005

LAST NAME FIRST NAME

{Page 18} STRUCTURE FOR COMPOUND F (show all H’s) [8 marks]

{Page 20} STRUCTURE FOR COMPOUND G (show all H’s) [10 marks]

{Page 20} What vibration is responsible for the 2400 cm-1 peak [ 1 mark]

{Page 22} TWO ISOMERS FOR COMPOUND H (show all H’s) [12 marks]

{Page 23} CIRCLE correct isomer [5 marks]

{Page 24} FORMULA FOR COMPOUND I: [1 mark]

{Page 25} STRUCTURE FOR COMPOUND I (show all H’s) [12 marks]

PINK DATA SHEETS FOR USE IN CHEM 213

c = 3 x 108 m s-1 h = 6.6 x 10-34 J s

N = 6 x 1023 k = 1.38 x 10-23 J K-1 R = 8.3 J K -1 mol-1

EJ = h2J(J+1)/8π2I

ν = (1/2π)(k/μ)1/2

ν = (γ/2π)Bo

NU/NL = e-x where x = ΔE/RT

I = m1m2r2/(m1+m2)

NUCLEUS 1H 13C 2D 11B 19F 31P 195Pt 29Si

MAGNETOGYRIC RATIO (() 27 7 4 9 25 11 6 5

I (spin quantum number) 1/2 1/2 1 3/2 1/2 1/2 1/2 1/2

% ABUNDANCE 100 1 0.02 80 100 100 34 5

Isotopic masses:

Precise masses of some common elements

atomic

weight

isotope mass % relative

abundance

atomic

weight

isotope mass % relative

abundance

H 1.00797 1H 1.00783 100 Si 28.086 28Si 27.9769 100

2H 2.01410 0.016 29Si 28.9765 5.10

C 12.01115 12C 12.0000 100 30Si 29.9738 3.35

13C 13.00336 1.08 P 30.974 31P 30.9738 100

N 14.0067 14N 14.0031 100 S 32.064 32S 31.9721 100

15N 15.0001 0.38 33S 32.9715 0.78

O 15.9994 16O 15.9949 100 34S 33.9679 4.40

17O 16.9991 0.04 Cl 35.453 35Cl 34.9689 100

18O 17.9992 0.20 37Cl 36.9659 32.5

F 18.9984 19F 18.9984 100 Br 79.909 79Br 78.9183 100

81Br 80.9183 98.0

I 126.904 127I 126.9045 100

Mass Spec Predictions

m/e fragment m/e fragment m/e fragment m/e fragment

M-1 H M-27 HCN M-41 C3H5 M-55 C4H7

M-2 H2 M-28 CO M-42 CH2CO M-56 C4H8

M-14 CH2 C2H4 C3H6 M-57 C4H9

M-15 CH3 M-29 CHO M-43 C3H7 C2H5CO

M-16 O C2H5 CH3CHO M-58 C4H10

NH2 M-30 NO M-44 C3H8 M-60 CH3CO2H

M-17 OH CH2O CO2 M-77 C6H5

NH3 C2H6 M-45 CO2H M-79, 81 Br

M-18 H2O M-31 OCH3 OC2H5 M-91 C6H5CH2

M-19 F M-32 CH3OH M-46 C2H5OH M-127 I

M-26 C2H2 M-35, 37 Cl NO2

( ) % . . .

( ) %( . ) ( . ) ( . )

.

M x y z

Mx y z

w

+ = + +

+ =+ +

+

1 11 0 016 0 38

211 0 016 0 38

2000 2

2 2 2

-BLANK PAGE-

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UNIVERSITY OF VICTORIA FINAL EXAMINATION ...web.uvic.ca/~chem213/213Fin-06.pdfCHEM 213 2006 Final Exam Page 6 Compound B, the smelly component emitted by pulp mills, showed M+ at m/z