Kinetics Simple Models

Kinetics: Differential Equations and Simple Compartmental Models
K. J. Kearfott Department of Nuclear Engineering and Radiological Sciences College of Engineering University of Michigan Ann Arbor, MI 48109-2104 (734) 763-9117 FAX (734) 763-4540 kearfott@umich.edu
Suggested Reading Cember: Chapter 4, pp. 195-196, pp. 299-308, pp. 315-320, pp. 550-554 Evans: Chapter 15 Krane: Sections 6.3-6.6 Lamarsh: Section 2.9 Moe: Chapter 2 Shleien: p. 3-14, 3-16 to 3-17, 12-7, 12-12 to 12-22 Turner: Section 3.12 Suggested Review KJK lectures: Activity and the Decay Law
Outline
Differential equations and compartmental models Simple cases of decay Pure decay Multiple loss terms (leaking tank) Decayed atoms as a compartment Decayed atoms as a compartment with multiple ! loss terms Production with decay General case of production with decay Different production terms Decayed atoms for production with decay Production with multiple loss terms Decayed atoms for production with multiple loss ! terms Maximums and steady states Maximum activity produced Steady state Atmospheric 14C Radiocarbon dating Production with gas mixing in a room Activation Simple activation Activation with burnup
Kinetics: Simple Models K. J. Kearfott

Sunday, September 11, 2011 Sunday, September 11, 2011
Differential Equation of Importance to HP

Most differential equations used in radiation protection are of general rst order linear form In fact, the most common differential equation is the simplest form of Bernoullis equation (n = 1) Once solved, the solution may be remembered and applied to almost all situations
Important DE, Contd.

Differential equation to be solved dy ( x ) + p(x)y( x ) = q(x) dx Solution
! p( x)dx # + p( x )dx & y(x) = e " e" q(x)dx + C ( %" $ '
where x : independent variable y(x) : dependent variable p(x) : function of x (no explicit y - dependence), unique to the equation of interest q(x) : function of x (no explicit y - dependence), unique to the equation of interest C : constant of integration, determined from boundary conditions (e.g. initial conditions)

Proof of Solution
dy ( x ) + p(x)y ( x ) = q(x) -(1) dx p( x ) dx Multiply by e ! , the "integrating factor" for this case dy ( x ) ! p( x ) dx p( x ) dx +e p(x)y ( x ) = e ! q(x) dx Note that (xy)'=x'y+y'x, thus e!
p( x ) dx
Summary: Most General Approach For Simple, First-Order Kinetics
-(2)
p( x ) dx dy ( x ) p( x ) dx y ( x )% = e ! + e! d ! p(x)dx y ( x ) ' dx & p( x ) dx p( x ) dx dy ( x ) p( x ) dx d "e ! y ( x )% = e ! + e! p(x)y ( x ) $ ' dx # & p( x ) dx dy ( x ) p( x ) dx p( x ) dx e! = d "e ! y ( x )% ( e ! p(x)y ( x ) -(3) $ ' dx # & Putting (3) in (2), and simplifying
d "e ! $ #
p( x ) dx
dy ( x ) + p(x)y( x ) = q(x) dx ! p( x)dx # + p( x )dx & y(x) = e " e " q(x)dx + C ( %" $ '
d "e ! $ #
p( x ) dx
p( x ) dx p( x ) dx p( x ) dx y ( x )% ( e ! p(x)y ( x ) + e ! p(x)y ( x ) = e ! q(x) ' &
p( x ) dx p( x ) dx d "e ! y ( x )% = e ! q(x) $ ' # & Integrate both sides of (4), and simplifying p( x ) dx y ( x ) %dx = ! e ! q(x)dx + C ' & p( x ) dx p( x ) dx e! y( x) = e! q(x)dx + C
-(4)
! d #e ! $
"
p( x ) dx
( p( x ) dx " ! p( x ) dx q(x)dx + C % y( x) = e ! $! e ' # &
-(5)
Sunday, September 11, 2011

Using the Solution

Put differential equation into the specic form for solution (using algebraic manipulations) Identify x [independent variable], y [dependent variable], p(x), q(x) Write down the solution Use other information (given) to solve for the constant of integration C; usually this information is in the form of initial (or boundary) conditions Alternatively, may evaluate the solution in terms of denite integrals
Writing the Equations for any Model

Identify all relevant compartments --radionuclides --physical locations --chemical form --physical form Include all inputs and outputs from each compartment, with appropriate connections among compartments Write an equation for each compartment (usually assume linear, rst order kinetics) Put equations into familiar format in order to solve Identify and use boundary (usually initial) conditions or other relationships to solve for the unknown constants in the solution Be sure the units are correct e.g. are atoms or activities being tracked?

Choosing the Model

Each compartment be correspond to a physical location, a chemical form, a radiological form, physical form, or some combination of variables Choosing the model may be the most difcult part of any general problem Often, several models may be utilized in the search for a model that best approximates the observed data Several books exist about compartmental models, some specic to the problems of biological systems [e.g. Friedman, Godfrey, Iyengar, Kajiya, Shipley]
Determining Parameters
Even if the model is well known, it still remains to chose the parameters that apply to the actual situation Model parameters may include a rate constant for transfer from one compartment to another, or the size of the compartments Input functions or initial conditions are sometimes not known and must be approximated Computer tting routines are most useful in determining model parameters

Complex Models and Fitting

Often models may be too complex to derive a simple analytical solution => Use computer tting techniques (either home-grown or commercially available) The appropriate model to t a given set of experimental data may not be known; nding the appropriate model is important and is often done by trial and error (user-friendly modeling software is becoming more available, e.g. Stella) Some problems involve determining the transfer constants for a given model, which may be obtained by tting data; in other cases these constants are derived from averages of observed data Problems may be divided into two broad types -Model known or guessed, want to predict time courses of amounts or concentrations (e.g. dose estimation due to internally deposited radionuclides), or -To obtain explanation of the data (e.g. medical radiotracer experiments)
Simple Decay
N(t)
!N(t)
Simple Decay, Contd.

simple decay dN (t ) = ! "N (t ) dt dN (t ) + "N (t ) = 0 dt Compare with the general form, for which solution is known dy ( x ) + p( x )y ( x ) = q( x ) dx x =t; y= N p( x ) = " ; q(x) = 0
! p( x)dx $ + # p( x )dx ' y(x) = e # q(x)dx + C ) &# e % ( ! "dt $ + "dt ' * N (t ) = e # &# e # 0dt + C) % (
Simple Decay, Result
N (t ) = e !"t [0 + C] = Ce ! "t If initial condition is given as N (0) = N0 , then for the above solution get N (0) = N0 = Ce! " 0 + C = N0 Putting this into our solution equation N (t ) = N0 e !"t
!1 = 0.01, !2 = 0.05, !3 = 0.1, !4 = 0.5 log [ N(t) ] = 1.0 * exp(-!t)
Graph on Semi-log Paper
Scaled (Normalized) Version
!1 = 0.01, !2 = 0.05, !3 = 0.1, !4 = 0.5 log [ N(t) ] = log [1010exp(-!t)]

Sometimes special selection of the axis variables results in a normalization so that it is not necessary to plot some of the variables. The above is an example of this.

Normalized Version: Semi-Log
Example of Simple Decay

Problem: C-11 decays with a half-life of 20 minutes. How long does it take for the amount of C-11 to reduce to 10% of the initial amount? Solution: A= Ao exp(- ! *t) => t = - ln (A/Ao) / ! Here ! = ln 2 / 20 min = 0.034/min Therefore have t = - ln (0.1) / (0.034/min) = 68 minutes
The above is true for any value of lamda!

Another Example of Simple Decay

Problem: The air turnover rate in a room is 15% per hour. How much is a given substance diluted in 2 hours?
Multiple Loss Terms: Leaking Tank

A tank is found to be leaking a fraction k of its volume per unit time. If the tank contains a solution with uniformly mixed radionuclide with a decay constant !, then write an equation describing the amount of activity in the tank as a function of time t. Let the initial number of atoms of radionuclide in the tank be denoted by No.
Solution: A= Ao exp(- ! *t) => A/Ao = exp(- ! *t) Here ! = 0.15/h Therefore A/Ao = exp[ - (0.15/h) * 2 h] = 0.74 = 74% In other words, the substance will be 74% of its original concentration after 2 hours.
Tank N(t)
!N(t)
kN(t)

Leaking Tank Solution
Leaking Tank, Easy Way

Fairly straight forward to identify that the effective removal constant is actually the decay constant plus the leakage constant (0.01) The answer may be written directly from the equation for simple decay; this works because the leakage is modeled as a very simple, rst order, linear process The same set of circumstances arises if activity is cleared from an organ in the body both by decay and by some physiological (e.g. transport, or metabolism followed by transport) process Note that the sum here is in terms of the decay or removal constant (NOT a half-life). The summed constant could be termed an effective removal constant
dN (t ) = ! "N (t ) ! kN (t ) dt dN (t ) + (" + k )N (t ) = 0 dt x = t ; y = N; p( x ) = " + k ; q(x) = 0 y(x) = e #

! p( x)dx
$ + # p( x )dx ' e q(x)dx + C ) &# % (
* N (t ) = e N (t ) = e
' # ( " + k )dt $ + # ( " +k ) dt e 0dt + C ) &# % (
!( " + k )t
[0 + C] = Ce !( " + k ) t
If initial condition is given as N (0) = N0 , then for the above solution get N (0) = N0 = Ce! " +k 0 + C = N 0 Putting this into our solution equation N (t ) = N0 e ! " + k t
Leaking Tank Results
Leaky Tank Results, Contd.

Example of Two Loss Terms

Problem: A radionuclide is in a room where the air is being continuously turned over. It reduced in concentration to 30% of its original in 4 hours. What is the effective half-life of the radionuclide in the room? If the radionuclide has a half-life of 7.5 hours, what is the air turnover rate in the room? How long will it take for half the air in the room to turn over?
Decayed Atoms as a Compartment

The number of decayed atoms may be treated as a compartment. The total number of atoms in the compartment represents the total number of decays, which is useful for dose estimation and for determining the number of counts for a detector The number of decayed atoms is equal to the number of stable progeny atoms
Solution: Although this is not a leaking tank, the problem is identical in that it has two loss terms. A= Ao exp(- ! *t) => ! = - ln (A/Ao) / t Therefore have ! = - ln (0.3) / (4 h) = 0.30/h The radionuclide decay constant is ! = ln 2 / 7.5 h = 0.09/h Thus, the room turnover rate must be 0.30/h - 0.09/min = 0.21/h In other words, the turnover rate is 21% per hour Half the air will be turned over in (ln 2) / (0.21/h) = 3.3 h
Radionuclide N(t)
!N(t)
Decayed Atoms D(t)
dN (t ) = ! "N (t ) dt # N (t ) = N0 e ! "t dD (t ) = + "N (t ) = " N0 e !"t dt

Decayed Atoms, Math
Compare to our known equation dD(t ) + 0 " D( t) = #N 0e $#t - (1) dt dy + p(x)y = q(x) - (2) dx % x = t ; y = D; p( x ) = 0 ; q(x) = #N 0e $#t - (3) Write the solution
$ p( x )dx ' +& p( x )dx y(x) = e & q(x)dx + C * )& e , ( + $ 0dt ' + 0dt $#t * - D(t ) = e & ) & e & #N 0e dt + C , ( +
Simpler Solution
The number of radioactive atoms at the beginning of the time period is given by N(0 ) = N0 The number of radioactive atoms at the end of the time period is given by N( t ) = N0 e !"t Since for every atom which decayed there is an atom of stable progeny created, the difference between the initial and final numbers of parent radionuclide is equal to the number of decays, i.e. D(t ) = N( 0) ! N(t ) = N 0 ! N0 e !"t = N0 (1! e ! "t ) This is the same result achieved previously. It is important that this particular solution ONLY works because the progeny is stable and there are no other source terms for the parent.
- (4) - (5) -
D(t ) = 1 & 1#N 0 e $#t dt + C = #N 0 & e $#t dt + C = $N 0e $#t + C If initial condition is given as D(0) = 0, then for the above solution get 0 = $N 0 + C % C = N 0 Putting this into our solution equation D(t ) = N 0 (1$ e
$#t
- (6) -
- (7) - (8) -
Note that D(t ) = N 0 $ N ( t), i.e. the number of decays is equal to the difference between the initial number of radioactive atoms and those which are left at any time (which makes sense).
Graph of Results
Semi-log Graph
!1 = 0.01, !2 = 0.05, !3 = 0.1, !4 = 0.5 N(t) = 100 [1 - exp(-!t) ]

Scaled Graph
Example of Decayed Atoms

Problem: Sr-90 is a bone-seeking radionuclide with a half-life of 28.8 years. Assume that once strontium is deposited in bone, and that it is not excreted biologically in any appreciable way. How many decays occur as a result of the uptake of 20 microCuries of Sr-90 in 1 year? In 50 years? Solution: Because of the assumption of negligible biological excretion, this is a case of simple decay. It is important to be careful with the unit conversions. Recall that A(0) = N(0) x ! Here, ! = ln 2 / 28.8 y = 0.024/y and A = 20 x 10-3 x 3.7 x 1010 dis/s x 3600 s/h * 24 h/d x 365 d/y = 2.33 x 1016 dis/y The total number of initial atoms is thus N(0) = A(0) / ! = (2.33 x 1016 dis/y) / (0.024/y) = 9.72 x 1017 atoms Now, nd number of decays Decayed atoms = (initial atoms) [1 - exp(-!t) ] For one year Decays = 9.72 x 1017 atoms [1 - exp(-0.024"1) ] decays/atom = 2.3 x 1016 decays (about 2% of the total) For 50 y Decays = 9.72 x 1017 atoms [1 - exp(-0.024"50) ] decays/atom = 6.8 x 1017 decays (about 1/3 of the total) In reality, the biological time course of Sr-90 in bone may be complex. It may enter blood after being trapped in the lungs from an inhalation, then be taken up in bone. It may deposit on the surface or at depth within in the bone (each with different biological excretion rates)

Decayed Atoms with Another Loss Term

Consider the situation in which we are interested in the number of atoms which decay in the compartment of interest, but there is another loss term from the compartment
Decays with Losses, Soln.

dN ( t ) = ! " N ( t ) ! kN ( t ) # N ( t ) = N 0 e! ( " + k )t dt dD ( t ) = + " N ( t ) = " N 0 e! ( " + k )t dt Compare to our known equation dD ( t ) dy + 0 $ D ( t ) = " N 0 e! ( " + k )t % + p(x)y = q(x) dt dx # x = t ; y = D; p ( x ) = 0 ; q(x)=" N 0 e! ( " + k )t Write the solution
! p( x )dx ' + & p( x )dx y(x) = e & q(x)dx + C * )& e , ( + ! 0dt + 0dt - D ( t ) = e & ' & e & " N 0 e! ( " + k )t dt + C * ) , ( +
Radionuclide N(t)
!N(t)
Decayed Atoms D(t)
kN(t)
D ( t ) = 1 ' & 1" N 0 e! ( " + k )t dt + C * = " N 0 & e! ( " + k )t dt + C ( +
" N 0 e! ( " + k )t + C "+k If initial condition is given as D ( 0 ) = 0, then " " 0=! N0 + C # C = N0 "+k "+k . " 1 Note that 0 represents the fraction of the / " + k3 2
=! losses that are decay. Putting this into our solution equation " N0 '1 ! e! ( " + k )t * D (t ) = + "+k(
Production with Decay

P N(t) !N(t)
Production/Decay, Contd.
If initial condition is given as N (0) = N0 , then for the above solution get P N (0) = N0 = + Ce "0 ! P # C = N0 " ! Putting this into our solution equation P $ P' + & N0 " ) e "!t ! % !( P N (t ) = N0 e "!t + (1 " e "!t ) ! Note that if N (0) = 0, N (t ) = N (t ) = P (1 " e "!t ) !
! atoms$ & P[=]# " time % dN (t ) = P ' ( N(t ) dt dN (t ) + (N (t ) = P dt x = t ; y = N; p( x ) = ( ; q(x) = P

' p( x)dx * + p( x )dx y(x) = e ) e) q(x)dx + C / ,) + . ' (dt * + (dt 0 N (t ) = e ) ,) e ) Pdt + C/ + .
N (t ) = e N (t ) =
'(t
[ P) e
(t
dt + C = e
' (t
* e (t P + C/ , ( + .
P + Ce ' (t (
Production/Decay Result
Semilog Graph
Production P = 0.02, 0.05, 0.1, and 0.5 Decay ! = 0.1 N(t) = P/! [1-exp(- ! t) ]

Scaled Graphs
Examples of Different Forms of Production Terms

The following are taken from Bevelacqua (2004). A key to avoiding mistakes is to continuously check for unit consistency.

Example of Production with Multiple Loss Terms

Problem: Derive an expression for N1(t) in the following model.
Solution, Production with Multiple Loss Terms

Solution: The compartments beyond the rst compartment have no inuence over it, so the problem is immensely simplied if are only concerned about the rst compartment.
k 1,other P1 k 2,other P2
N1(t) k 1,2 N2(t) k 2,3
!1
k1,other
!1
!2
k1,2
k 3,other P3
N3(t) k 3,4
* * *
!3
dN1 ( t ) = P1 ! ( k1,other + "`1 + k1,2 ) N1 ( t ) dt This is identical to the problem just solved (production and one loss term) except could define "effective = k1,other + "`1 + k1,2 The solution thus has the same form, namely P N(t) = 1-e- " t " P $1 ! exp ! ( k1,other + "`1 + k1,2 )t & # N1 (t) = ' ( k1,other + "`1 + k1,2 ) %
Pn
k n,other
k n-1,n Nn(t) !n k n,n+1

** A generalization of this situation will be made in KJK Lecture on Long Chains

Maximum Possible Activity Produced

One approach => Consider the activity equation with P representing the production rate expressed as atoms/time, i. e. A(t) = ! N(t) = P x [1-exp(- ! t) ] As t => innity, exp(- ! t) => 0, and A(t) approaches a maximum. At the maximum A(max) = ! N(max) = P x [1- 0 ] = P In other words, the maximum possible activity is equal to the production rate (in atoms/time)! Another approach is to look directly at the differential equation describing the situation, namely (on a number of atoms basis) dN/dt = P - !N For a maximum, slopes are zero, i.e. dN/dt = 0 Thus 0 = P - !N(max) = P - A(max) #A(max) = P This is the same result, which is reassuring.
Approaches to Steady State (Equilibrium) Problems

Write the general temporal solution to the problem, then set the time very large to get the steady state Write the general differential equations, then set the differentials equal to zero. Solving will yield the answer directly! This is usually the simplest approach.

Example: Atmospheric
14C
Atmospheric 14C, Solution

" activity % ' Let PA = !P (activity production rate)[=]$ # time & Using our production/decay equation (activity basis) P Aatm (t ) = A (1 ( e (!t ) ! For t ) *, (1 ( e (!t ) ) 1 " 15 Bq % $ 1.4 , 10 ' PA y & # + Aatm (* ) = = = 1.15 , 1019 Bq " ln 2 % ! 14 C $ ' # 5700 y & Another approach (atom basis) dNatm (t ) P = ( ! 14 C N atm (t ) + P = ( ! 14 C Natm (t ) + A dt ! 14 C At steady state 0 = (! 14 C Natm ( SS) + + Aatm ( SS) = PA ! 14 C
The production rate of 14C in the atmosphere is 1.4 x 1015 Bq/y. What is the steady state global inventory of 14C?(problem 4-39 in Cember). Note:
14N
(n, p)
14C
Here, we are given PA, the production rate on an activity basis. The problem is nothing more than a simple production/decay problem (just solved previously). Note that a steady state is reached for long times t, in fact we want N(t) for t=innity. The half-life of 14C is 5700 y (from RHH), thus we have all we need to solve. Note that the box represented here is the 14C in the atmosphere (no losses other than decay are assumed).
PA
Atmosphere Natm(t) A atm(t)
!A atm(t)
PA = 1.15 , 1019 Bq ! 14 C

Example of Production with Decay and Steady State [Lamarsh Problem 3.4, p. 220]
Problem: The $-emitter 28Al (half-life 2.30 min) can be produced by the radiative capture of neutrons by 27Al. The 0.0253 eV cross-section for this reaction is 0.23 b. Suppose that a small, 0.01-g aluminum target is placed in a beam of 0.0253 eV neutrons, % = 3 x 108 neutrons/ cm2-s, which strikes the entire target. Calculate (a) the neutron density in the beam (in neutrons/cm3) (b) the rate at which 28Al is produced (in atoms/s) (c) the maximum activity (in microCuries) that can be produced in this experiment Recall that energy and velocity are related. At thermal energies (0.0253 eV) the neutron velocity is 2200 m/s. Other possibly useful information 1 barn = 10-24 cm2 density of Al = 2.7 g/cm3 Avogadros number NA = 6.02 x 1023 atoms/mole Natural Aluminum is 100% Al-27 1 Ci = 3.7 x 1010 dis/s Note: Burnup of the Al-27 will be neglected here.
Solution
!=
ln 2 0.693 = = 0.301 / min = 0.00502 / s T1/2 2.3min
" ( thermal ) = 0.23 b= 0.23 x 10 -24 cm 2 n # = 3 x 10 8 2 cm $ s 0.01 g Al Thermal 0.0253 eV % 2200 m/s
a) Neutron density & n ) #( 2 = neutron density x neutron velocity ' cm $ s + * & n ) & cm ) = n( 3 + , v( ' cm * ' s + * n ) & 8 ( 3 x 10 + ' # n cm 2 $ s * -n = = = 1364 m ) & 100 cm ) v & cm 3 ( 2200 + ( + ' s *' 1m *

Solution, Contd.
Solution, Contd.
!"N (Al-27)
N (Al-2 8)
#N (Al-2 8)
(b) Rate at which Al-28 is produced dN Al-28 ! atoms of Al-28 $ # & = production - losses % dt " s ) , . Al-28 atoms produced ! incident neutrons $ + . N Al-27 ( atoms of Al-27 ) = '# &( + 2 " % + cm s ! incident neutrons $ . Al-27 atoms # &. + " %cm 2 * ! Al-28 decays $ / 0# N ( Al-28 atoms ) " Al-28 atoms-s & Al-28 % The production term is ! 3 x 10 8 n $ ! 0.23 x 10 -24 Al-28 atoms-cm 2 $ P= # &1 Al-27 atoms-n " cm 2 s & # %" % ) ! 23 atoms Al-27 $ , + ( 0.01 g Al-27 ) # 6.02 x 10 mole Al-27 & . " % + . g Al-27 $ ! + . 26.98 # & + . " mole Al-27 % * =15,396 Al-28 atoms s
(c) Maximum activity in microCuries The maximum occurs when there is a steady state, and the production term is equal to the decay term. In other words, the maximum ctivity is equl to the production term dN / dt = 0 = production - losses = P - decay = P - A ! A = N" = P atoms Al-28 & # A ( max ) = % 15, 396 ( $ ' s # Bq & # & # 10 6 Ci & Ci )% $ decay / s ( % 3.7x1010 Bq ( % Ci ( '$ '$ ' = 0.42 Ci

Radiocarbon Dating
Suppose the ratio of C-14 to elemental carbon in a given type of living object, say wood, is well known and hasnt changed over time Further assume that the amount of C-14 in the atmosphere is known, and easier still, has remained constant over time If the amount of C-14 is xed in a living object upon its death (e.g. tree cut down and a board sawed), except for decay, then the age of the object (approximately time of death of the organism) may be determined from the following simple equation (current ratio of C-14: C in object) = (ratio of C-14: C in object at time of death) * exp [ - ln (2) * (time since death) / (half-life of C-14) ] A good website for information about this method is
Example of Radiocarbon Dating

For the determination of the age of an artifact using C-14 dating, the ratio of C-14 to stable carbon in the object is then compared to the ratio of C-14 to stable carbon found today. There are several assumptions, however, which must be made for C-14 dating in its simplest implementation. Additional information Half-life of C-14: 5715 years C-14 decays 100% of the time via beta emission Production rate of C-14 in the atmosphere: 1.4 x 1015 Bq/y Percentage of total carbon that is C-14: 10-10 % Percentage of total carbon that is C-13: 1.07 % Percentage of total carbon that is C-12: 98.93 % Avogadros number: 6.02 x 1023 atoms/mole Atomic weight of carbon: 12.0107
C-14 is produced from the following reaction Atmospheric N-14 + cosmic neutron => C-14 + proton A piece of wood found at an archeological site is analyzed. For a counting period of 20 minutes, at an efciency of 72%, there were 423 beta counts recorded corresponding to C14. It is then determined that the sample contains 1.57 g of carbon. Approximately how old is the sample (expressed in years)?
http://www.c14dating.com/

Solution
ln 2 != = 1.213 " 10 #4 / y 5715 y activity of C-14 in sample = C $ yt 423 counts decays = = 29.375 min counts ( % emission ( % ' 0.72 * '1 * ( 20 min ) & emission ) & decay ) A = ! decays ( % 60 min ( % 24 h ( % 365 d ( % ' 29.375 *' *' * & & ) min ) & h ) & d ) ' y *
Some Questions about Radiocarbon Dating

What effect will changes in atmospheric C-14 production have on the results, and how may a correction be made for this? How could any losses or additions of C-14 to the object following its death be accounted for? For a given measurement sensitivity and error, what will be the uncertainty in the estimation of the age of the object due to the measurement uncertainties alone? If other radionuclides are used for this technique, then how will half-life inuence accuracy and the ages which may best be determined using the method? What other factors may inuence your comments?
atoms of C-14 in sample =
(1.213 " 10
#4
/y
= 1.273 " 1011 atoms C-14
(1.57 g ) '
atoms of C in sample =
% 6.02 " 10 23 atoms ( * mole & ) = 7.876 " 10 23 atoms C % 12 g ( ' & mole * )
1.273 " 1011 atoms C-14 % C-14 ( = = 1.616 " 10 #13 ' * 23 & C ) sample today 7.876 " 10 atoms C % C-14 ( % C-14 ( % C-14 ( =' e# !t + ' e# !t ' * * & C ) sample today & C ) sample yesterday & C * living today ) - % C-14 ( 0 /' C * & ) sample today 2 2 # ln / / % C-14 ( 2 /' C * & ) living today 2 . 1
,t =
% 1.618 " 10 #13 ( # ln ' * 10 -12 & ) = = 15, 025 y + 15, 000 y #4 1.213 " 10 / y

Criticisms of RadioDating by Anti-Evolutionists

See evolution-facts.org or Ferrell (2001) Problems with all dating methods 1. Each system has to be a closed system. Nothing can contaminate any of the parents or the daughter products while they are going through their decay process. No piece of rock cannot for millions of years be sealed off from other rocks, water, chemicals, and changing radiations from outer space 2. Each system must initially have contained none of its daughter products. This can in no way be conrmed. 3. The process rate must always have been the same. The decay rate must never have changed. All radioactive clocks, including C-14, have always had a constant decay rate unaffected by external inuences. This is not true because decay rate may be changes if a) material is bombarded by high energy particles from space; b) there is a nearby radioactive material emitting radiation, c) as a result of physical pressure, d) as a result of contact with chemicals 4. Changes in the blanket of atmosphere surrounding the planet would affect results by changing the amount of cosmic radiation 5. Any change in the Van Allen belt would change the amount of cosmic radiation 6. Things started at the beginning, no daughter products were present, only elements at the top of the radioactive decay chain were present
Criticisms Specic to C-14 Dating

The following assumptions 1. Atmospheric carbon is constant 2. Oceanic carbon is constant 3. Cosmic radiation is constant 4. Rate of formation and decay of C-14 is constant 5. The decay rate of C-14 has never changed 6. Nothing has ever contaminated any specimen containing C-14 7. No seepage of water or other factor has brought additional C-14 to the sample since death 8. The fraction of C-14, which the living thing possessed at death, is known today 9. The half-life of C-14 is accurate 10. Nitrogen is the precursor to C-14, thus nitrogen in the atmosphere must have been constant 11. Instrumentation is precise, working properly, and analytic methods are always carefully done 12. Technique always yields the same results on the same sample or related samples that are obviously part of the same larger sample 13. The earths magnetic eld was the same in the past as it is today

Production Term with Gas Mixing in a Room Suppose a radioactive gas is leaking from a container into a room of volume V at some rate L (atoms/time). Suppose that the turnover rate of air in the the room is R (fraction of volume/time). Write an equation for the activity concentration in the room as a function of time. (Assume instantaneous and complete mixing of room air). The compartment represents radioactive atoms in the air of the room. Losses are both by decay and by removal with air leaving the room. Entrance is through leakage from the container.
Gas Mixing, Soln.
Problem on a "number of atoms" basis dN (t ) = L ! RN (t ) ! "N (t ) dt = L ! (R + " )N (t ) For N(0) = 0 L # N (t ) = 1 ! e !( R + ") t R+" On an activity concentration basis A(t ) "N (t ) "L = = 1 ! e !( R + ") t V V V( R + " )
Room Air L(atoms/time) N(atoms) A(activity) V(volume) RN !N
Note that this expression is the same as that obtained for production with decay, but substitute (R + " ) = " effective everywhere for " and use L for the production term (previously P).

Simple Activation
Suppose a radionuclide is produced by bombarding a target which produces a radionuclide. This is also a simple case of production/decay (if we neglect the burnup of the target). The compartment is the amount of product actually present at any time
Simple Activation, Soln.

activation problems Rate of interactions = flux ! cross section # & cm 2 ! interactions # particles& ( ! )% "% ( 2 $ cm sec ' $ bombarding particles ! target nuclei ' # & interactions = ") % ( $ sec ! target nuclei ' The cross section is a probability of interaction per bombarding particle flux per target nucleus. It is a property that has been measured and is tabulated in the RHH and the "Barn Book" (1 b = 10-24 cm2 ). Production rate of product is thus
!"Ntarget
Product Nproduct
#Nproduct
# & interactions P = ") % ( ! Ntarget ( target nuclei ) $ sec ! target nuclei ' interactions& % ( = ")Ntarget # $ ' sec If N target is constant, then our previous equation for simple production/decay applies, and we have P +* t Nproduct (t ) = 1 + e p roduct * product
Nproduct (t ) =
")N target 1 + e +* product t * product
The maximum product for simple activation occurs for t , -, or t large w.r.t. the product half - life, and is equal to ")Ntarget Nproduct (t maximum = t- ) = * product
Activation with Burnup

Suppose that there were a nite number of target atoms for an activation, and we wanted to account for the effects of losses of these atoms during the activation process. Our model is now a two-compartment model.
Solution
Production rate of product varies as f(t), i.e. # interactions & ( P = !" Ntarget (t )% $ ' sec We therefore have, for the target compartment dN target (t ) = ) P = )!"N target (t ) dt This is the same form as simple decay, with the solution Ntarget (t ) = Ntarget (0 )e )!"t Our equation for the product compartment is dN product (t ) = P ) * Nproduct (t ) = !"N target (t ) ) *N product (t ) dt Substituting in our equation for Ntarget (t ) dN product (t ) = !"Ntarget (0 )e) !"t ) * Nproduct (t ) dt Now, put in form we know the solution to
Target Ntarget
!" Ntarget
Product Nproduct
#Nproduct
dN product ( t )
dt Compare to Bernoulli' s equation Write down the solution
+ *N product ( t ) = !"N target ( 0)e )!" t

)!" t
x = t ; y = Nproduct ; p( x ) = * ; q(x) = !"N target ( 0)e

) p( x)dx , + + p( x )dx / y(x) = e + q(x)dx + C 1 .+ e 0
) *dt , + *dt / )!" t 2 Nproduct (t ) = e + . + e + !"Ntarget ( 0)e dt + C1 0

Solution, Contd.
Simplifying yields Nproduct (t ) = e ! "t #$N target (0) % e"t e !#$ tdt + C
( ) & ) e " ! #$ t = e !"t (#$N target (0 ) + C+ " ! #$ ' *
Activation with Burnup Results
]
Accounting for target burnup, have Nproduct (t ) =
Nproduct (t ) = #$N target (0)
e !#$t + Ce ! "t " ! #$
!"Ntarget (0 )
If initial condition is given as N product (0) = 0, then for the above solution get
(#
product
$ !" )
e $!"t $ e
$# product t
#$N target (0) Nproduct (0) = 0 = +C " ! #$ #$ Ntarget (0 ) " ! #$ Putting this into our solution equation
,C=! Nproduct (t ) = #$N target (0) Nproduct (t ) =
Neglecting target burnup, have !"N target Nproduct (t ) = 1 $ e $# product t # product
#$Ntarget (0) !"t e !#$t ! e " ! #$ " ! #$
#$N target (0) !#$t (e ! e !"t ) (" ! #$ )
Important note: For activation with target burnup, the saturation or maximum activity is not reached. Furthermore, in the case that the number of target atoms is small, this effect is even more pronounced.
where " = " product Recall that neglecting burnup (i.e. for the conditions for which " >> #$ and - #$t - 0) we got the following #$N target !" t Nproduct (t ) = 1 ! e product " product

Graph of Results
Proof that Total Activation Is Always Less with Burnup Present than Without It
!" N (1 $ e$ #t ) # !" N $!" t Activity with burnup A B = ( e $ e$ #t ) # $ !" For simplicity, let % & !" Check that A B < A !" N $!" t ( e $ e$ #t ) < !" N (1 $ e$ #t ) # $ !" # Simplifying the above 1 1 ( e$% t $ e$ #t ) < # (1 $ e$ #t ) # $% Perform algebraic manipulations
Activity without burnup A= (1) (2)
(3)
(4)
# e$ % t $ # e$ #t < ( # $ % ) $ ( # $ % ) e$ #t # e$ % t < ( # $ % ) $ ( # $ % ) e$ #t + # e$ #t # e$ % t < ( # $ % ) + % e$ #t # e$ % t $ # < % e$ #t $ % # (e$% t $ 1) < % (e$ #t $ 1) # 1 $ e$ #t < % 1 $ e$ % t

Note that if # <% , then (5) (6)
# < 1. % Also, if # <% , then (1 $ e$ #t ) > (1 $ e$% t )
%&1 = 0, %&2 = 0.01, %&3 = 0.05, %&4 = 0.075 ! = 0.1 Nproduct = 100/(! + %&) [ exp (- %&t) ' exp ('!t) ]
1 $ e$ #t >1 (7) 1 $ e$ % t Equations (6) and (7) imply that equation (5) must be true for # <% # Similarly, if # >% , then > 1. (8) % Also, if # >% , then 1 $ e$ #t < 1 $ e$% t '
) (
1 $ e$ #t ' <1 (9) 1 $ e$ % t Equations (8) and (9) imply that equation (5) must be true for # >% Finally, if # =% , then there is no burnup.
Maximum for Activation with Burnup

N product (t ) =
!"N target (0)
(#
product
(e $ !" )
$!"t
$ e $# product t
Note on Steady State, Equilibrium, and Saturation

If times are long with respect to the decay constant, and either complete decay or buildup occurs, then there is a substantial simplication of formulae ==> At steady state, equilibrium, and saturation, the [ 1 - exp ( - ! t ) ] terms approach one
Differentiate w.r.t. time, and set equal to zero to find the time of maximum product dN product (t ) =0 dt !"N target (0) = $!"e $!"t max + # producte $ #product tmax (# product $ !" )
)
Under such circumstances have the following Activity produced (and present) Total number of decays A/! P/!
% !"e $!"tmax = # product e
$# product t max
!" # product
=e
( !" $ #product )t max
& !" ) ln ( + = (!" $ # product )tmax ' # product * & !" ) ln ( + ' # product * = (!" $ #product )
, t max
The maximum is thus equal to N product (t max ) =
!"Ntarget (0) $!"tmax $# t e $ e product max (# product $ !" )
)

Hints on Solving Kinetics Problems

Be sure that the units match up whenever any equation is used Be careful with equations; they may be stated either on an activity or on an atom basis Often an equation may be written simply based upon an understanding of the overall form expected for the solution (e.g. exponential, 1-e-kt, what the maximum should be, etc.) Always verify that the conditions for which the equation was derived apply to the situation at hand
Summary of Kinetics Formulae: Decay
Simple decay N (t ) = N0 e !"t Decay with another loss term N (t ) = N0 e !( " + k )t Decayed atoms D(t ) = N0 (1 ! e! "t ) Total possible number of decays D(# ) = N0 Decayed atoms with another loss term
"N 0 ( ) 1 ! e! " + k t " +k Total possible number of decays when loss term
D(t ) =
D(t ) =
"N 0 " +k
Summary of Kinetics Formulae: Production
Summary of Kinetics Formulae: Activation
Production without decay N (t ) = Pt Production with decay P N (t ) = (1 " e "!t ) ! Production with decay, with initial activity P N (t ) = N0 e "!t + (1 " e "!t ) ! Steady state for production and decay P N (SS) = ! Production with additional loss terms P ( ) N (t ) = 1" e " ! + k t (! + k )
Activation, neglecting target burnup !"N target $# t N product (t ) = 1 $ e product # product
Steady state (or maximum) activation product !"Ntarget N product (SS ) = # product Activation, with target burnup N product (t ) =
!"N target (0) $!"t $# t e $ e product (# product $ !" )

Things to Know
Radiocarbon dating assumes that C-14: C ratio is constant in living objects, that C-14 in the atmosphere has been constant over time, and that objects no longer exchange carbon with the environment (and there are not C-14 production terms) once the object is no longer living
Denitions to Know
activation Bernoullis equation boundary conditions buildup compartment cross section decay decay chain decay constant dependent variable determinant dual decay eigenvalue equilibrium rst order linear differential equation ssion products ux half-life independent variable initial conditions

Denitions, Contd.
matrix solution of system of equations nonlinear equations parent radionuclide partial decay constant progeny radionuclide radiocarbon dating radiation intensity rate transfer constants saturation specic activity steady state target burnup
Exercises
Write the set of differential equations corresponding to any rst order linear model Solve simple sets of equations involving differential equations of simple form Recognize simple decay and decay with production problems and be able to solve quickly

Suggested ABHP Part II Problems

1975: 1976: 1978: 1979: 1981: 1982: 1983: 1984: 1986: 1987: 1988: 1989: 1990: 1991: 1992: 1993: 1994: 6a+b, 16 2a, 8a 1d 1a+b+c, 7(know what MPC is) 1a+b, 7a, 12a+c 10a 13a+b 2a+b 1a+b 5a+b, 8a+b 9f+g+h 5a+b, 7a+c+e, 10b+c+d+e+f, 11b+c+d 1a+b, 3d, 4a+b, 8f+g, 9 11a+b+d 1, 9a+b, 10a, 12a 8a+b+c, 12a+b 7a+d
References
Bevelacqua, J. J. Production equations in health physics, Radiation Protection Management, vol. 20, no. 6, pp. 9-14, 2004. Cember, H. Introduction to Health Physics,Third Edition, McGraw-Hill, New York, NY, 1996. Ferrell, V., The Evolution Cruncher, Evolution Facts, Inc., Altamont, TN, 2001 Friedman, M. H., Principles and Models of Biological Transport, Springer-Verlag, New York, NY, 1986. Godfrey K., Compartmental Models and Their Application, Academic Press, New York, NY, 1983. Iyengar, S. S., Computer Modeling of Complex Biological Systems, Chemical Rubber Company Press, Boca Raton FL, 1984. Kajiya, F., Kodama, S., Abe, H., Compartmental Analysis: Medical Applications and Theoretical Background, Karger, New York, NY, 1984 Krane, K. S. Introductory Nuclear Physics, John Wiley and Sons, New York NY, 1988.

References, Contd.
J. R. Lamarsh, A. J. Baratta, Introduction to Nuclear Engineering, 3rd Edition, Prentice Hall, Upper Saddle River, NJ, 2001. H. J. Moe, Operational Health Physics Training, Argonne National Laboratory, ANL-88-26, U.S. Department of Energy, National Technical Information Service, Springeld, VA 22161. Shipley, R. A., Clark, R. E., Tracer Methods for in Vivo Kinetics: Theory and Applications, Academic Press, New York NY, 1972. Skrable, K., French, C., Chabot, G., Major, A., A general equation for the kinetics of linear rst order phenomena and suggested applications, Health Physics 27: 155-157, 1974. Stella II, software from High Performance Systems, 45 Lyme Road, Hanover NH 03755, telephone (603) 643-9636, fax (603) 643-9502, AppleLink: X0858 Radiological Health Handbook (RHH 1970), U.S. Dept. of Health, Education, and Welfare, 1970.
References, Contd.
B. Shleien, L. A. Slaback, B. K. Birky (RHH 1998), Handbook of Health Physics and Radiological Health, Third Editions, Williams and Wilkins, Baltimore, MD, 1998. Tuli, J. K., Nuclear Wallet Card, National Nuclear Data Center, Brookhaven National Lab, Upton, NY, 1990. J. E. Turner, Atoms, Radiation, and Radiation Protection, Pergamon Press, New York, NY, 1986.

Kinetics Simple Models

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Kinetics: Differential Equations and Simple Compartmental Models

Kinetics: Simple Models K. J. Kearfott

Kinetics: Simple Models K. J. Kearfott

Differential Equation of Importance to HP

Important DE, Contd.

Kinetics: Simple Models K. J. Kearfott

Kinetics: Simple Models K. J. Kearfott

Summary: Most General Approach For Simple, First-Order Kinetics

p( x ) dx p( x ) dx p( x ) dx y ( x )% ( e ! p(x)y ( x ) + e ! p(x)y ( x ) = e ! q(x) ' &

( p( x ) dx " ! p( x ) dx q(x)dx + C % y( x) = e ! $! e ' # &

Kinetics: Simple Models K. J. Kearfott

Using the Solution

Writing the Equations for any Model

Kinetics: Simple Models K. J. Kearfott

Kinetics: Simple Models K. J. Kearfott

Choosing the Model

Kinetics: Simple Models K. J. Kearfott

Kinetics: Simple Models K. J. Kearfott

Complex Models and Fitting

Kinetics: Simple Models K. J. Kearfott

Simple Decay, Contd.

Simple Decay, Result

!1 = 0.01, !2 = 0.05, !3 = 0.1, !4 = 0.5 log [ N(t) ] = 1.0 * exp(-!t)

Kinetics: Simple Models K. J. Kearfott

Graph on Semi-log Paper

Scaled (Normalized) Version

!1 = 0.01, !2 = 0.05, !3 = 0.1, !4 = 0.5 log [ N(t) ] = log [1010exp(-!t)]

Kinetics: Simple Models K. J. Kearfott

Kinetics: Simple Models K. J. Kearfott

Normalized Version: Semi-Log

Example of Simple Decay

The above is true for any value of lamda!

Kinetics: Simple Models K. J. Kearfott

Kinetics: Simple Models K. J. Kearfott

Another Example of Simple Decay

Multiple Loss Terms: Leaking Tank

Kinetics: Simple Models K. J. Kearfott

Kinetics: Simple Models K. J. Kearfott

Leaking Tank Solution

Leaking Tank, Easy Way

dN (t ) = ! "N (t ) ! kN (t ) dt dN (t ) + (" + k )N (t ) = 0 dt x = t ; y = N; p( x ) = " + k ; q(x) = 0 y(x) = e #

$ + # p( x )dx ' e q(x)dx + C ) &# % (

' # ( " + k )dt $ + # ( " +k ) dt e 0dt + C ) &# % (

Kinetics: Simple Models K. J. Kearfott

Leaking Tank Results

Leaky Tank Results, Contd.

Kinetics: Simple Models K. J. Kearfott

Kinetics: Simple Models K. J. Kearfott

Example of Two Loss Terms

Decayed Atoms as a Compartment

Decayed Atoms D(t)

dN (t ) = ! "N (t ) dt # N (t ) = N0 e ! "t dD (t ) = + "N (t ) = " N0 e !"t dt

Kinetics: Simple Models K. J. Kearfott

Kinetics: Simple Models K. J. Kearfott

Decayed Atoms, Math

!1 = 0.01, !2 = 0.05, !3 = 0.1, !4 = 0.5 N(t) = 100 [1 - exp(-!t) ]

Kinetics: Simple Models K. J. Kearfott

Kinetics: Simple Models K. J. Kearfott

Example of Decayed Atoms

Kinetics: Simple Models K. J. Kearfott

Kinetics: Simple Models K. J. Kearfott

Decayed Atoms with Another Loss Term

Decays with Losses, Soln.

Decayed Atoms D(t)

) dt , + dt / )!" t 2 Nproduct (t ) = e + . + e + !"Ntarget ( 0)e dt + C1 0