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1968
Recommended Citation
Lee, Bong Kyu, "Neutron activation analysis applied to arsenic determination " (1968). Retrospective Theses and Dissertations. 3488.
https://lib.dr.iastate.edu/rtd/3488
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TABLE OF CONTENTS
Page
I. INTRODUCTION 1
V. APPLICATION 86
I. INTRODUCTION
NQ + a ^ N^ + b
where
N^ = the target nuclei,
NQ(n,y)N^
rays from the product, N^^ can be measured, and the intensity
irradiation.
The choice of a suitable irradiation facility is based
ously with the samples and treated under the same laboratory
B. Review of Literature
The value of activation analysis as a research tool was
5
sented for the first time in the United States the technique
a great share of the credit for the success of the Oak Ridge
papers (20, 23, 44, 45, 82, 124, 146, 147, 148, 149) presented
(71), fundamental concepts and techniques (5, 31, 40, 70, 101,
separating many elements from a single matrix (2, 17, 73, 151),
medical use.
generators.
activation analysis.
66, 134, 140, 141, 142), (b) solvent extraction of Asl^ into
ppm in 1957, and well agreed with Holland, hut Guthrie et al.
C. Objective of Investigation
A. Activation Equations
0mN°fff
R = <2-1)
where
2
0 = the neutron flux (n/cm -sec),
activation,
gm-atom),
isotope.
D = \N* (2-2)
where
N* = the number of atoms of the radioactive nuclide in
the sample,
^= R - D =
0mN°far
= M - • (2-3)
B^act N -X?!
N* = set. (1_ g I) ^ (2-4)
-XT
= XN* = 0Cact.N(l-e ). (2-5)
-XTj -XT^
^T; = 0^act.^(l-e )(e ^) . (2-6)
\ = • (2-8)
becomes constant.
following equation;
MA^
m = Zyjf— ' (2-10)
not constant, and the flux and the activation cross section
cadmium ratio.
N*. For isotopes of very large cross sections and long ir
then be given as
0c* N*
N** = , (2-11)
in which
-XT 0.693T_
An = A- e = A„ exp(- — -) (2-13)
D I I
or
-XT_ -XïL
At = )(s ) (2-14)
equation
M
m = (2-15)
(6.023 X 10^3)00^^^ s e ^
e ^1 , (2-16)
% I
= N* e ^ (2-17)
^2 ^
N - N = N (e )(l-e
Dl \
0CT t °.693TQ 0.Ô93T -T
~ —0 693 ^(exp(- = ))(l-exp(- )) (2-18)
u.byj Ty
or
m =
(N -N )(M)(0.593)
\ % :
0.693Tj^ 0.693(Tj^ )
(6.023 X lo23)(Ty)(0aact.%SXexp^- ijr -))(l-exp(- -))
(2-19)
(N_ - N )
% %
in Equation 2-19, the weight of the element in the sample
can be obtained.
\ '
-\(T -T )/2
* * * 19
N -N = N e ^ X(TL -Tn ) . (2-20)
^2 ^1
= XNU e ^ ^ . . (2-21)
\ '
-w• — •
From Equations 2-22 and 2-23, the left side of equations are
eliminated to form
0.693(T _T )
^eff. - 0.693 T|^ (2-25)
If
TD, - TDi = Tj
The effective time is, in this case, slightly less than the
given by
R, =
N
2 A/
i+1 ^
-XT) -XT
N.0.O-.(1 - e J ^ e
— ]—]—J —27^
~ N -X.T_ -X.T--*
2 N.0.ff.(1 - e )e
i=l ^ ^ ^
result:
and
= 0 . (2-29)
24
N -X T T
2 K,(\. -\.)(l-e ^)e ^^ = 0 (2-30)
i=l ^
and
33As'^^(n^y)33As'^^ .
times.
9
In most cases. Be has been used as the target element,
since it has the low neutron binding energy, 1.7 Mev, and
Mev and 5.5 Mev. Various energy losses from sources of the
to
to
a,n
Ac2"-Be9 a,n 22 y .
a,n 1622 y.
Po21°.Be9 a,n 138 d.
1.9 y.
y/n . 50 d.
gets.
The choice of activating particles naturally depends on
nuclei.
actor are its large size and high cost. Present day nuclear
priate sections.
31
type.
rates and shorter resolving times than were possible with the
spectrometry.
ing from the container well as are the smaller crystals, for
medium, Nal(Tl) crystal, may remain the same for many appli
the detector will also vary with the other decay scheme
variables.
cident photon and the binding energy of the shell from which
the electron was ejected. However, some of the energy is
tion.
37
10
Ag X Ray
22 kev
10'
0.08 Mev
10
•CD Iodine
c Escape
c
Peak
10-
w
4-1
a
0
o
u
10'
10'
10
25 50 75 100 125
Channel Number
If this were the only process for energy loss, the response of
10 Photoelectric + Compton
+ Pair Production
10
-1
p,(Cm"
10 Total
Photoelectric
Compton
-1
10
lpair
Productio:
-2
10
10 10 10
Energy, kev
Figure 3-2. Gamma-ray absorption coefficients in Nal(Tl) for
various gamma-ray energies (135)
40
Ec (3-1)
E (3-2)
0.6612 Mev
Ba K X Ray
10-" -
lO^f-
10-
10'
25 50 75 100
Channel Number
137
Figure 3-3. Gamma-ray spectrum of C
42
tions.
total-absorption peak. •
and 1.368 Mev. The single-escape peak at 2.25 Mev and the
1.368 Mev
xiiscape Single
Escape
2.75 Mev
I—i 10-
•qj
c
g
to
4
co
-t-)
api
8
10'
10"
0 25 50 75 100 125 150 175 200 225 250
Channel Number
Figure 3-4. Gamma-ray spectrum of Na24
45
only on the energy of the gamma ray, the nuclear and physi
Since this peak arises from the shield material and not from
46
(c) gamma rays which scatter out of the crystal enter the
low energy.
Gamma rays in the energy region below 200 kev are de
ray (28 kev) will be lost and an additional peak will appear
47
tered radiation, but may also come from the source holder,
which results from the Compton electrons, one can see a def
of a graded Pb shield.
bremsstrahlung effects.
10"
0.51 Mev
Annihilation
Radiation
10'
10
i—t
0
c
s
ih
4
cq 10- Sum
•p 0.51+ Backscatter
g
5
10'
Breirtsstrahlung
1.02 Mev
10"
10 100
25 50 75
Channel Number
.45
Figure 3-5. Gamma-ray spectrum of Ti (51)
51
I = N^2T (3-4)
rss
the sum spectrum occurring, N the input pulse rate, and T the
resolving time.
seen with Equation 3-4, the intensity of the random sum spec
5. Bremsstrahlunq effects
bremsstrahlung.
53
emissions.
G = k(Z E) (3-5)
k = 0.33 X 10 ^ Mev"^.
o
The percentage of bremsstrahlung may be much higher in
50 75 100 125
Channel Number
radium families,
ground gamma rays which strike the crystal have had their
and then for a small crystal, and then compares the ratio of
Pre-irradiation
Assay
Irradiation
Non-destructive Destructive
Analysis Analysis
Radioactivity
Measurement
Data Evaluation
50
A. Pre-irradiation Assay
B. Irradiation of Samples
of radioisotopes:
C (4-1)
s
with
3 (4-2)
fs 1
and
52
ao (4-3)
where
absorption,
2200 m/sec,
a sphere,.
sample
=0 = (4-4)
and
1
(4-5)
1+CÙ
with
(4-6)
and
63
1 G - 2^1 ^ (4-7)
where
^0 ~ 1+CÛ (4-9)
with
CÙ = 0.34 (4-10)
^tr °
where
C. Non-destructive Analysis
Guinn and Wagner (49) and others (4, 22, 55, 70, 85)
7 2
for two hours at thermal neutron flux 5 x 10 n/cm -sec. The
D. Destructive Analysis
tion.
(2) let the carrier and the element in the sample be in the
compound.
E. Radioactivity Measurement
Weight of X in sample
Weight of X in standard
the test analysis, the chances for success are greater, since
F. General Limitations
relation to others.
rare gases He, Ne, and A, are well analyzed for special cases.
72
H. Physical Limitations
cases where samples are bigger than the rabbit tube in which
I. Chemical Limitations
J. Nuclear Limitations
affected. When this happens, the neutron flux may fall off
the large irradiation capsule may also limit the size of the
sample.
K. Interfering Reactions
nuclei ,
constituents with
yA yA+4
Z+1 Z+2
Reactions Examples
1. Principal reaction
33As7S(n,y)22As7G
3. Primary interferences
gjSe^^(n,p)
35®^^^(n,a)ssAs^^
Table 4-1 (Continued)
Reactions Examples
3. Secondary interferences
4. Second-order interferences
14Si3°(n,Y)i4Si31 g-i5p31(n,y)isp32
y( n ,Y)y+i( n ,y)y+2
Z+y^''(Y'P)zX''(n,Y)y+l (y'PjggAs^^(n,y)23As^°
z+y*"(Y.p)y
79
cause the effective fluxes and cross sections for fast neu
trons are usually much less than those for thermal neutrons.
2. Secondary interferences
particles, and the ratio of the cross sections for the pri
dN
af = - NlA-l (4-11)
dNg
dF = BiXi - «200*2 (4-12)
dN^
= - NLX_ (4-13)
"dF ~ " "3^2
dN^
= (4-14)
dt "3^2
1 Z-1^'
2 for
4 for .
- 1) (4-15)
provided
and t » .
^1
M. Experimental Feasibility
V. APPLICATION
A. Sample Preparation
Samples
The standard
in early 1967.
State: semi-metallic
2 3
Outer electronic configuration; 4S 4P
3 O ,O O 4- R
Radius; Crystal, As" 2.22 A; As 0.69 A; As (AsO^)
0.47 A
Ionization potential: _ 10 ev
Representative compounds:
0; As
-3; ASH3
75
b. Nuclear properties of As (78)
Abundance (percent): 100
Aa^^(n,y) As^^
(1). Half-life
26.4 h. (62,78)
26.1 h. (7)
26.3 h. (102)
26.8 h. (102)
27.0 h. (150)
69
As 15 m Ge^^(p,2n)As^^
89
As^^ 52 m. Ge"^^(d,2n)As^*^
Ge72(d,2n)As72
Ge^^(d,2n)As^^, As^^(n,2n)As^^
75
As Stable 100% natural abundance
Fission
Se®^(d,an)As^®
76
As
(26-Shi
B" % McV
i ! 2 O- 309
2 1 O O' S30 2 656
3 O•6 O 853 II 2 434
! 11 '
4 O -2 O •952
1 !> !1 ; I2
S 2 •i i • Ml
•n 2-Oi3
6 6 -9 1 '• 7 4 8 H "il !1 11 " i f r — - Î -733
7 35 2 •405
i 1 !
S 53 2 •965 !1 1
Ref. i . G.Bdckstrom. I . Markluno.
S
1
1
11!
11
217
A r k i v . f o r F y s i k ; 17 3 9 3 I 9 6 0 1
2. N.N. O c l y o g i n , A . A . S o r o k i n . 1 1 1
Zhur. E k s i T c o r e t . F y s . 3 3 ! I 0 6
7 Y i Vf V O 559 2''
1
i960
^/l-
' w h o s e decay scheme i s s l i r h i l y
different^ l ^ se"! . '
91
10
0.56 Mev
0.66 Mev
10
10
100 200 300 400
Channel Number
92
a' § •h i
Leè'i .
#:
r'i '2
î'f ^ CO
.e 1 V
Z-^ ^
Pg:i_r P:#
âi&f< %13: w
ga!?L '
Ada:<'ik Mi
i3,r Eii 1 ^
%,
a#'-S'é :.
êLîi
<sp^s %;uS'ffi*? %: !
e#mu
liaaiHk'irr 1
BsSS
s ;W =1? a«2i
1 W#
js»#:
o 3> 51
0(^ bj«1 :j i=l
Sr Sreo
l.7h 0*Sr29m81 Sr25d82 Sr33h83 Srau84 JT 8564d sres 2 Sr eh 87^102 Sr 83 Sr504389'" Sr28*90 Sr97«91^
-
1 |?a>
Br 65m 49.46
79909 ti*
93 r/ S '
rU.2J (•3> yU.&4
m i f" ., , à •<
Se
7836 ^Se44m70 Se 71 See.4d72 «m % Se(20d75^ Se79?'
asm 7«I0 y 57m% 81''- «•I0)'fi04} 69sSe 8325m rSe3m84 rSe39i85
""HP- r^-
0-
7Tjm J C. Cl« w % J A
As Asœ As15m69 /kjo As62h71^ As26h72'- As76473^ 8sAs1 I8d 74'- 30lAs7s % As265h76*"• As39h77^ As 78 As9m79 As15»80 As33s61
9im i-i2.lî-U As 65
74.92t6 Hw'/aliî-ir OH IT ,0s*.0i40) »•»*.•• r # rftaM.ao-4s
,U,M-ZX
ri* r
w
Q43>
C«M CM w ECO *
94
Samples
decay time.
Samples coded 1 through 33 were irradiated separately
10 2
at 0 = 6 X 10 n/cm -sec for one hour, two samples and one
C. Discussion
5
10
0 = 3 X 10 n/cm -sec
= 10 min.
2.5 kev/chn
0.84 Mev
T =2 hrs. 29 min
T =5 hrs. 24 min
10
3
2
10
100 200 300 400
Channel Number
Figure 5-1. Gamma-ray spectrum of sample 17-102
99
10-
T 10 9
T
0 = 1.2x10 n/cm -sec
= 10 min.
= 5 min.
2.5 Tcev/chn.
0.84 Mev
10
iH
CD = 2 hrs. 20 min.
G
C
fd
m
4J
c
I
=10 hrs. 29 min.
10 2
0 =3x10 n/cm -sec
Tj = 2 hrs.
T = 10 mm.
0.2lMe\
0.56 ivtev 10 kev/chn.
0.80 Mev
1.36Mev
1.SoMev
T =28 hrs
2.29 Mev
^ 52 min
iH
<u z.45 Mev
G
C
rd
4 2.80 Mev
m
-P
c
8
T =97 h
^ 54 min
3.50^fev
T =156 hrs
^ 09 mi
10'
Extrapo1ated
(D
+J
C
S
Q.
g 10-
W
4J
C
•
g Estimated
u Photopeak Area
10'
10'
10'
1.5 2 2.5 3 3.5 4 4.5 5 5.5
Half-life of As'^ (1 = 26.5 Hours)
Figure 5-5 Determination of half-life of As^o found in sam
pie 27-101 and optimization of decay time
Figure 5-6. Gamma-ray spectfa of sample 20-1 and arsenic
standard 17
104
O-
:
/
h
105
r4
m
c
§
(5 io3
10'
100 200 300 400
Channel Number
Figure 5-7. Gamma-ray spectra of sample 19
2".
Inside Inside Length
Diameter Sample Container
UP I.N
OUT
Ki^tron
0
01
LEFT RIGHT
CENTER
1.38" 3.81'
Inside H Inside T.ength
Diameter Rabbit Tube
•a
Q)
N
•H X
rH P
(0 fH
UP CENTER DOWN
Foil Location
•o
0)
O
a LEFT CENTER RIGHT
Foil Location
g
iH
k
Id
0)
N
•H
iH
i
g
CENTER OUT
Foil Location
10
100 hr
10 Ohr
Ohr
10 10hr,
-1
10
5 hr
-2
10 Ihr
10-3
0) 10-4
m 10-5
•H
-5
10
> 10-7
•ri
-8
< 10
10-9
10-10
-11
10
10-12
10-13
KT^KT^^icr^Kr^icr® icr® icr"^ icr^ lO"^ i(T^ icr^ icr^ icr^ icP lo-
Sensitivity (grains)
00
A 6.3
B 6.3 7.7
C 8.6 9.0
D 7.0 7.9
E 8.1 9.4
F 5.9 6.3
G 6.3 6.8
ensure the poison safety of the analyst and others, and the
technique.
2. Discussion of results
of useful application.
of time.
Figure 5-3.
10 2
to be irradiated at thermal flux of 0 = 6 x 10 n/cm -sec
ing power level of the UTR-10 reactor. The one hour irradia
pressed 16.5% and 29.1% at the OUT end. The UP end was de
pressed by 2.3% and 1.2% at the DOWN end. Two and half
at 0.56 Mev and 0.66 Mev, which is another gamma ray energy
that As^^ emits. The ratio of peak count at 0.56 Mev to the
count at 0.66 Mev was 3.45 for samples and 3.56 for the
short decay times and the counting statistics for long decay
it was decided to use data taken at 3T|^, 3.5T|^/ and 4T^ for
the cigarette sample spectrum and the lower one shows that
ing formula:
75 ""
Amount of As in the sample
75
Amount of As in the standard
the sample and the standard was the same. Therefore, the
completely eliminated.
in ppm is ± 6.18%.
76
A sensitivity of As is established by utilizing
half-lives of As^^.
#
125
A. SiirriTiary of Investigation
B. Conclusions
10 2
tron flux of 0 = 6.0 X 10 n/an -sec, and = one hour.
can be developed:
spectively.
the Compton edge, the angle and time coincidences, the sum
peak, and the single and double escape peaks. To the best
Chapter III.
at all times.
Irradiated Samples Detection Post-irradiation
Cooling and and Sample
Storage Counting Storage
System
Central
Irradiation Control
Facility Console
Digital
Computer
Unit
Data Storage
Pre-irradiation and
Sample Storage Date Library
Sample Flow
Control
Data Flow
I
135
VIII. ACKNOWLEDGMENTS