Transport Phenomena: Giulio Lolli

Modern Methods in Heterogeneous Catalysis Research
TRANSPORT PHENOMENA
10/31/08
Giulio Lolli
Outline
2
Part I - Theory
Why
Transport?
Fundamental equations
Unified approach to transport phenomena
Boundary Layer approach
Dimensionless numbers
Part II - Practice
Example:
Methanol Synthesis
Transport Phenomena
10/31/08
Further Reading
3
Part I
Bird,
Steward, Lightfoot
Transport
Phenomena
Asano
Welty
Mass Transport
Fundamentals of M,H&M Transfer
Part II
Handout
Web:
Perrys
Document DB # 15375
Chemical Engineering Handbook

Transport Phenomena
10/31/08
Part I
Theory
Transport Phenomena
10/31/08
Why Transport? Catalytic Process

5
Thermodynamic
Reaction
Equilibrium
Phase equilibrium:
adsorption/desorption
Kinetic
Reaction
Kinetic
Transport
Reactants/Product
to/
from the active sites
Heat to/from the
Transport Phenomena
active site
10/31/08
Transport Phenomena
6
nx
Type of transport
What is transferred
Specific direction x
Momentum Transport
!xy
!uy
=
x
Heat Transport
Kinetic Energy
T
CA
qx = k
jA,x =Law
DA
Newtons
x
x
Thermal Energy
1 Law (Fluxes)
T
CA
qx = k
jA,x = DA Fouriers Law
x
x
!
!Transport
! Chemical
! A
T! Mass
= !
u
!q = k T
j!A =Energy
DA C
CA
jA,x = DA
Ficks Law
x
st
! =
! A
!
! A
!q = k T
j!A = DA C
Transport Phenomena
2nd Law (variation in space-time)
10/31/08
!xy =
First
Law
of
transport
7
!uy
!xy =
x
!
uy
!xy =
x
1st Law (Fluxes)
st
1 Law (Fluxes)
!
!u
T! = !
!
!u
T! = !
! =
! A
qx
st
1 q =Law
T (Fluxes)
k
j = D
x
x
T
qx = k
x
A,x
CA
A
xA
C
jA,x = DA
!!
!u
T!q ==kT
!
!
j!
! A
= DA C
! A
j!A = DA C
!q =
!
!q = k T
! =
! A
! =
! A

D!u
!
= 2!u+!g p
nd Transport Phenomena
Dt
D!
u
2
!
= !u+!g p
Dt
Law (variation in sp
10/31/08
Math 101- Gradient

8
Math 101 Nabla, Gradient

S
x
S
!
!
= y S = y

S
z
Math 102 Divergence, Laplacian

S
x
Vx Vy Vz
!
S ! !
!
= y S = y V =
+
+
x
y
z

S
z
2
Transport Phenomena
10/31/08
! =
! A
Dt
= !u+!g p
Second
Law
of
Transport
2 Law (variation in space-time)
nd
DT
2
D!u
Navier-Stokes
=
k T +u
!
p
= !u+!g C
p
Dt
Dt
DT
2 Fouriers
C
= k T + rH
DCA
Dt
2
=
D
C
+
r
DC
A
A
A
= D C + r
2 Fick
Dt
Dt
D
=
D
Dt
2
=
Fundamental equations of the system
Dt
rxn
nd
nd
D!u
!
= 2!u+!g p
Dt
Fundamental equations
Transport Phenomena
10/31/08
S
!
!
= y S = y

Math 102 Divergence & Laplace
10
S
z
Math 102 Divergence, Laplacian

S
x
Vx Vy Vz
!
S ! !
!
= y S = y V =
+
+
x
y
z

S
z
2
2
2
S
2
!
!
S = S =
+ 2 + 2
2
x
y
z
Math 103 Substantial Derivative

S
x
Vx Vy Vz
!
S ! !
!
= y S = y V =
+
+
y 10/31/08
z

Transportx
Phenomena
2
2
2
S
2
!
!
S = S =
+ 2 + 2
2
x
y
z
11

S
x
Vx Vy Vz
!
S ! !
!
= y S = y V =
+
+
x
y
z

S
z
2
2
2
S
2
!
!
S = S =
+ 2 + 2
2
x
y
z
DS
S
S
S
S
S
!
=
+ !u S =
+ ux
+ uy
+ uz
Dt
t
t
x
y
z
Transport Phenomena
10/31/08
Dt
= 2
Equations of Motion
12
Fundamental equations of the system

D!u
2
!
= !u+!g p
Dt
DT
2
Cp
= k T +u rHrxn
Dt
DCA
2
= DA CA +A r
Dt
! (!u) = 0
Transport Phenomena
10/31/08
Example
13
Start-up in circular tube

Cylindrical
coordinates
Only vz(r) 0
Example: startup in circular tube only uz (r) != 0

!
"
!
uz
u
1
uz
z
!
+ uz! = p +
r
t
r r
r
! z
In S.S. conditions (/t = Transport
0)
Phenomena
10/31/08
Example
Example: startup in circular tube only u (r) != 0
z
14
!
uz
u
z
!
+ uz! =
t
! z
1
p +
r r
uz
r
r
"
In S.S. conditions (/t = 0)

!
"
uz
p
r
=
r
r
r
uz
p r"2 A"
r"
=
+ "
r
2 "r
p r2
uz =
+B
4
$
p # 2
2
uz =
R r
4
B.C.
B.C.
uz
= f inite
r
uz = 0
Transport Phenomena
r=0
r=R
10/31/08
vz/vmax(r=0)
1.0
0.5
0.0
-1.0
0
0.0001
0.001
0.01
0.05
0.1
0.2
0.5
infinite
-0.8
-0.6
-0.4
-0.2
0.0
r/R
15
Transport Phenomena
10/31/08
0.2
0.4
0.6
0.8
1.0
Numerical Solution
16
Finite elements approach

Software packages
Fluent
CFD
Physics
Set up the correct problem and boundary conditions

Many times is not necessary to know the exact T,C,v
of every single point in your system
Transport Phenomena
10/31/08
Boundary Layer
17
All the phenomena happen in the boundary layer

Everything
outside the boundary layer is in equilibrium

and constant
The boundary layer is very thin

The
size of the boundary layer () is smaller than the

characteristic size of the system
Order of magnitude approach
Taylor
series
Transport Phenomena
10/31/08
Reynolds Number
18
Boundary layer approach

Reinolds Number
D"u
= 2"u
Dt
u
!
u
!
!
u
!
x
2
! "2
= 1/Re
x
ux
Prandtl Number
ux
Re =
ux
Re =
Transport Phenomena
10/31/08
= 1/Re
ux
Prandtls Number
ux
Re =
Prandtl Number
19
uT = uT /
DT
Cp
= k2 T
Dt
1/2
!
!
T
T
!
!
Cp uT
k 2
x
T
T
k
Cp u
2
x
T
! "3
T
k
Cp
T
P r1/3
Cp
Pr =
k
Cp
Pr =
Transport Phenomena 10/31/08
k
Dt
!
!
T
T
!
!
Cp uT
k 2
x
T
Schmidts Number
20
Cp
Pr =
k
T
k
Cp u 2
x
T
! "3
T
k
Re1/2
Cp
T
P r1/3
As usual everything is
the same
Schmidt Number
C
Sc1/3
Cp
Pr =
k
DA
Sc = D
Sc =

A
Transport Phenomena
10/31/08
Nusselts Number
21
Considering the
the fluxes:
fluxes:
Considering
T
T
= k
k
= hT
hT
qq =
=
x
x
!
!
T
!
T
! k!
!
T
!
hh!
T
k
TT
hx
x
hx
x
Nuu =
=
TT
kk
!"#$
!"#$
!"#$ !"#$
1/2
1/3
Re1/2
Prr1/3
Re
P
In general
general
In
KA x
x
Sh =
DA
C
!"#$
!"#$
Re1/2 Sc1/3
Transport Phenomena
10/31/08
Sherwoods Number
22
Considering the
the fluxes:
fluxes:
Considering
T
T
= k
k
= hT
hT
qq =
=
x
x
!
!
T
!
T
! k!
!
T
!
hh!
T
k
TT
hx
x
hx
x
Nuu =
=
TT
kk
!"#$
!"#$
!"#$ !"#$
1/2
1/3
Re1/2
Prr1/3
Re
P
In general
general
In
KA x
x
Sh =
DA
C
!"#$
!"#$
Re1/2 Sc1/3
Transport Phenomena
10/31/08
hx
x
Nu =
k
T
!"#$
!"#$
In General
Re1/2 P r1/3
23
In general
hx
KA x
1/3
Nu =
= f (Re) P r
Sh =
= f (Re) Sc1/3
k
DA
1/2
Re
Plate in laminar flow
2 + Re1/2
Sphere in laminar flow
f (Re) =
0.8
0.005Re
Packed bed in turbulent flow

Extension to macroscopic balances
)
*
*
Q =
q dA = A U T
1/U =
1/h +
s /k
Extension to Macroscopic Balances

24
Transport Phenomena
10/31/08
hx
KA x
1/3
Nu =
= f (Re) P r
Sh =
= f (Re) Sc1/3
k
DA
25
1/2
Re
2 + Re1/2
f (Re) =
0.8
0.005Re
Packed bed in turbulent flow
Overall Transfer Coefficient

)
*
*
Q =
q dA = A U T
1/U =
1/hi +
si /ki
A
1/U = 1/hint + s/kmetal + 1/hext

Transport Phenomena
10/31/08
Nu =
hx
Nu =
= f (Re) P r1/3
k
26
1/2
Re
2 + Re1/2
f (Re) =
0.8
0.005Re
= f (Re) P r
k
KA x
Sh = = f (Re) Sc1/3
D
A
1/2
Re
Plate
2 + Re1/2
Sphere
f (Re) =
0.8

0.005Re
Packed
flow
Packed bed in turbulent
Log-Mean Temperature Difference
Extension to macroscopic balanc

)
Q=
q dA = A U T
)
A
*
*
Q =
q dA = A U T
1/U =
1/hi +
si /ki
A
T1 T2
Tln =
ln (T1 /T2 )
Transport Phenomena
10/31/08
Conclusions
27
Momentum, Heat and Mass Transfer

Highly
inter-correlated
Similar
physical principles
Similar driving force
Similar mathematical formulas
2nd
order PDE numerical solutions

Highly dependent from fluid-dynamic properties
Simplifications
Boundary
layer
Dimensionless numbers
Transport Phenomena
10/31/08
28
PART II
Methanol Synthesis
Transport Phenomena
10/31/08
Methanol Production
29
Produced from SynGas

Catalyst
Cu/ZnO-Al2O3
Equilibrium limited
P
= 50 100 bar
T = 200 300 C
Main Commodity
20
Million ton/year
Typical plant size is 1 Million ton/year

12
m3/s
Transport Phenomena
10/31/08
Catalyst specs
30
KATALCO 51-8
Methanol Synthesis Catalyst
Long life as a result of the optimized formulation incorporating a patented
use of a fourth component MgO
Product Benefits
Low operating temperatures minimize the catalyst sintering rate
High catalyst selectivity gives very low impurities in the crude product
Close approach to equilibrium is achieved and maintained
Easy to reduce and start-up
Product Uses
Synthesis of methanol from H2, CO and CO2 mixtures arising from steam
reforming of hydrocarbons, coal gasification or POx
General
Description
KATALCO 51-8 is a copper catalyst on a ZnO-Al2O3 support with a MgO

promoter
Physical Properties (Typical)
KATALCO 51-8
Cylindrical pellet
5.4 mm
5.2 mm
1250 kg/m 3
80 kgf
Form
Diameter
Length
Bulk Density
Crush Strength
(axial)
Shipping &
Handling
Chemical Composition (Typical)

CuO:
Al2 O3 :
ZnO:
MgO:
64 wt%
10 wt%
24 wt%
2 wt%
Avoid contact with skin and clothing. Avoid breathing dust. Do not take
internally. Please refer to the relevant Material Safety Data Sheet for
further information.
KATALCO 51-8 catalyst is available in non-returnable polythene lined

mild steel drums or bulk bags for easy loading.
Transport Phenomena
10/31/08
Reactor types
31
Transport Phenomena
10/31/08
Multi-Bed Reactor
32
6:96
)";<=>=?@=<A)>=BC
)DEBFGHBG)@HGC)IAE>JKLDHGFM
6:27
6:25
6:24
N!C'$
6:29
6:26
6:67
6:65
6:64
6:69
6:66
456
476
866
896
846
#OPQ
856
Transport Phenomena
876
566
596
10/31/08
Reactor dimensioning
33
!"#$%&'()*+',"-#)
1 m/s
! wanted gas velocity
m2 section approx 4 m diameter

#JKG<H
Approx 7 m tall
12
2244
2444
;44
L<E)3
:44
!<'$)=>?@ABC
944
L<E)6
844
744
344
L<E)5
644
544
L<E)2
244
4
4
D<E)@<FGHI)=>C
Transport Phenomena
10/31/08
!"#$%&'()'*+,-%'.,+/'+.'*&01-2+,'"2'.$230"+2'+.'4&5'5&601)'
!"#$%&'()*+',"-#)
!
Pressure Drop
34
-56789:;86<) =>87) ?:@@:=) A56B5;CD=856) =>:) ?;:77E;:) 9;5?) DA;577

E786<)=>:)B5@@5G86<)B5;CE@DHI)
)
$# $
%
' %( "
%"
%"
)
) %&"$ ! %
*
&$ !
#" '
+ %'(&& # ,
,
& # ' " !% ( $ ! " . ' "
/
)
P
7QR) $F) 87)=>:
J>:;:)2)87)=>:)7E?:;B8A8D@)CD77)K:@5A8=L)M34)N<OC
To have 1 bar pressure drop
D
=
5
mm
=>:)<D7)C8V=E;:)9:678=L)M34)N<OCUQR) %p)87)=>:)K87A578=L)M3SUU)34WH)
?:@@:=)98C:67856)M4S44H)CQS)
)
+:7E@=7)=>D=)#4X)YP44)*DOC)X)4S4YP)FD;OC)
)
%69)A56789:;86<)34)C)@:6<=>)
! ) !"#!
)
1<)E5)E7>8)7)B=>=BCB)5<<=6=5>6:)I78)845)J5D=>>=>D)A<)845)?5768A
B7K=BCBL)A<)MGN)845)B7K=BCB)#4=595)BA@C9C;);4AC9@)J5)OPQ3
)
!"#$%&'()*+',"-#)
! At least 85% catalyst
*%&' +&'!
!%&' % +
)
, ( -()$%%
#45)67879:;8)5<<=6=5>6:)=;)?59785
efficiency
)
)
$
# # !
-A>;=@5?=>DQH)
"% "'
& $( )
)
! ) !"#! *
)
*%&' % ()(* 0.1
2" &'! 3
1<)E5)E7>8)7)B=>=BCB)5<<=6=5>6
= 1.7
B7K=BCBL)A<)MGN)845)B7K=BCB
+ &'! % $+,( 2" #
R = 0.5 mm
0
)
)
$
4
*%&' +&'!
,!.! % %
% $((# 0.1 #
!%&' % +
)
0
5 +6
, ( -()$%%
"
-,/$%% % *)-. 7 & , 0
)
3
Transport Phenomena
10/31/08
-A>;=@5?=>DQH)
)
Internal Mass Transfer Limitation
35
+ &'! % $+,(
!"#$%&'()*+',"-#
)
)
0#
)
!
$
4
!"#$%&'()*+',"-#)
,!.! % %
% $((# 0.1 #
0 =>:)! ?;:77E;:) 9;5?) DA;577
5 ?:@@:=)
+6 A56B5;CD=856)
-56789:;86<) =>87)
H"
E786<)=>:)B5@@5G86<)B5;CE@D
36
0
-,/$%% % *)-. 7 & , I)
#45)67879:;8)5<<=6=5>
3
)
)
)
$#" $
%
$
# # !
' % ( +5;C98;)+RSPGBB)
"% "'
& $( )
%"
%
) "
! ) !"#! *
)
T567C;5)7);U45?=679)U7?8=695)A<)O)BB)=>)@=7B585?)E=99)>
) %&"$ ! %
*
)
&$ !
#" '
+ %'(&& 7);8?C68C?5@)67879:;8)E=84)U59958);=X5)A<)7JAC8)G)BB)E=8
# ,
1<)E5)E7>8)7)B=>=B
,
& # ' " )!% ( $ ! " . ' "
/
B7K=BCBL)A<)MGN)8
)
)
J>:;:)2)87)=>:)7E?:;B8A8D@)CD77)K:@5A8=L)M34)N<OCP7QR)* $F)+87)=>:
!%&' % + %&' &'! WH
))
=>:)<D7)C8V=E;:)9:678=L)M34)N<OCUQR) %)87)=>:)K87A578=L)M3SUU)34
, ( -()$%%
?:@@:=)98C:67856)M4S44H)CQS)
)
)
Q
!
+:7E@=7)=>D=)#4X)YP44)*DOC)X)4S4YP)FD;OC) -A>;=@5?=>D H)
!
)
)
#45)U76V=>D)<768A?)A<)845)J5@)@?AU)@AE>)<?AB)SPQY)IU7
%69)A56789:;86<)34)C)@:6<=>)
*%&' % ()(* 0.1
Pressure Drop
2
3
$
)*+
,#, 0.005Re0.8
!
Packed
bed in turbulent
flow

*XTZ)FD;)G8=>)*
4X)H4)FD;)
)
4
$
/'
)
/
'
-.
'
Extension
to macroscopic
balances
"'/&
[786<)D)+E7>86<);86<)=>:)?;:77E
2)*+ & )*+3"
)*+
37
)
)
*
*
)Extension to macroscopic balances
#5)=:KD@ED=:)
Q = -56789:;86<)
q dA = A U T
1/U
1/hi =>:)
+ :V=:;6D@)
si /ki CD77
\
) and Sherwood Numbers
A
Nusselt
Colburn Factors
BDA=5;7
I) *
*
)
Q=
q dA = A U T
1/U =
1/hi +
si /ki
)
&A2'
1/U = 1/hint
+"s/kmetal + 1/hext
.(
+, '
' #(0"
$"'* ("')%&
$
#
/
'
01
'
+,
% T2
'
T
1
2)*+ 3,#,
$!
Tln =
% 3"1 /T2 )
)
ln
(T
-. '
'
"'$*$
)
T1 T2
4
$
/'
#
Tln =.
/- '
-. '
ln (T1 /T2 )
2)*+ & )*+ 3")*+
"'/&
%
01 '
' "')#%
)
J& '!56.
J
h = 725 2
h = 610 2
-56789:;86<)
m sK
) m sK J
J
)
725 2
h =mol
610 2
)h =mol
m sK
& 2' " m sK
k = 13.2
k
=
65.6
)
+, '
#(0"
2'
m2 s
m
s
%
)
mol
mol
Transport
Phenomena
10/31/08
k = 65.6 2
)k = 13.2 m2 s
% 3"
ms
'
External properties
% / ! )%)(' # 1 ! (') %
)
* " -)
External Limitations
38
)
#7;)?@A5?=?)B5CC;:;DE;)F;6G;;D)67;)H@<)@DB)67;)I;>>;6)<=:C@E;
)
+'
&7+,- ! $ 234 % ! 5+,- &/ 56
! #%')
(1
+ ' 5+,&.+,- !
! (%#* , " .
($ .
8941
No external limitations in terms of gas composition

&/ 56 ! *&/ ))) %
*0#
and temperature
profile
5+,-
! Due
)%)* *0#
to the
turbulent
flow regime
$( 234
)
#7;)?@<<)6:@D<C;:)5<)D96)@D)5<<=;M)9D>K)67;)7;@6)6:@D<C;:)<6@:6<
67;)75H7)7;@6)9C):;@E659D)5DJ9>J;BN)
)
Heat Exchanger
39
1st bed 580 490 K

35
MW power to take out

Boiling water to produce low pressure steam
16
Shell
!"#$%&'()*+',"-#)
kg/s steam produced

!
tube heat exchanger: 2 (5cm) tubes
hout=220
W/m2K
W/m2K
200
6:96
)";<=>=?@=<A)>=BC
)DEBFGHBG)@HGC)IAE>JKLDHGFM
6:27
6:25
6:24
6:29
N!C'$
6:26
6:67
6:65
6:64
6:69
6:66
456
476
866
896
846
856
876
566
#OPQ
Transport Phenomena!"#$%&'()'*&+,-"./'0+-1'"/'-1&'2'3&45'.6'-1&'%&+,-.%)'
10/31/08
596
Evaporation/condensation
5-22
HEAT AND MASS TRANSFER
40
For example, vapori

radiation and conve
result of heat absorb
the disengaging sur
when the superheat
also occurs from falli
flashing of liquids su
Pool boiling ref
heating surface is su
is not flowing at any
motion of the bubbl
of pool boiling are p
fluid temperature is
collapse of the bubb
pool boiling, with bu
resulting in net vapo
The general shape
to " tb, the tempera
temperature and the
metric relations tha
boiling curve was ori
[ J. Soc. Mech. Eng.
one of the great dile
faced with at least s
Pr water 7
Dukler plot showing average condensing-film coefficient as a function of physical properties of the condensate film and the terminal Reynolds
number. (Dotted line indicates Nusselt theory for Reynolds number < 2100.)
[Reproduced by permission from Chem. Eng. Prog., 55, 64 (1959).]
FIG. 5-10
1/2 Phenomena
1/2
Transport
hl / kl !l1/2 = 0.065(N
Pr)l Fvc
2
10/31/08
(5-99a)
Heat Exchanger
41
1st bed 580 490 K

35
MW power to take out

Boiling water to produce low pressure steam
16
Shell
kg/s steam produced
tube heat exchanger: 2 (5cm) tubes
W/m2K
U 200 W/m2K
hout=220
Low
pressure steam 1-2 atm 120C
Tln=
140K
Exchange Area 1300 m3 (about 2000 tubes)
40 banks of 50 tubes (4-5 m in size)
Transport Phenomena
10/31/08
Further Reading
42
Part I
Bird,
Steward, Lightfoot
Transport
Phenomena
Asano
Welty
Mass Transport
Fundamentals of M,H&M Transfer
Part II
Handout
Web:
Perrys
Document DB # 15375
Chemical Engineering Handbook

Transport Phenomena
10/31/08
$
$ ,
'
+
!
%
# &'()&*
+
)&'#)&
$
.& , ,
"
#$
'#2
+
+
+
"!
%
&&' 0& * $
%
"/
)&'1&&
+
) *
) *
),*
+
+,
+
!!
# !$
- . /0, 1
- . /3 1
- +3/4 1
! ,
6/
! ' 1! '
6!! &/
7$ # $
!
5
!
#
85 !!
'!(
2
2
2
"
&
! $ # $!
!"
!!
),* (
! '
! &$
5 !!$ ! !
$ /
!
!! '
9 :;
!&
&
&$6
! !&
!! " $
"
55
8 /
&$
&
/>>
>/3=
>/3=
>/3>
>/3>
>/?=
>/?=
>/?>
>/?>
>/4=
>/4=
>/4>
>/4>
>/0=
>#
=> #
>> #
>> #
>/0>
>/==
>/=>
>/0>
>/==
>/=>
<=>
=>>
==>
0>>
0=>
@9A
14
!!
$
&
/>>
>/0=
'!(
6 5
) +, - *
) *(
$!
& &$6
! !
5
5 !!$
" '
5
! " $! 6 9
7$
&!
& 6$
!! '
&9
"5
/
:;
!"
$!. 1
# 7$
$&
&$
! !&
!!
&
85 !!
$! 6
'! (
'
& 6$
>/
>/
>/>
>/>
.,
.,
.<
.<
!$ !
7$ # $
:;
"
.=
.=
< > <<> <0> <?> =>> = > =<> =0> =?> 0>> 0 > 0<> 00>
@9A
B
!/
'
=D
?D
4<D
,D
7$ # $
6&
!
&
C! ! &
'!(
5 !
$!
!5
& &
!"
! !C!
<
&
!
6 !&
/
6 !
& 6$ ,/
<
$
!
! 5 !! #
"5
&
! &
!
5 !
!
C
! &
$
&
# 5 !
5
7$ # $
>/<>
>#
=> #
>> #
>> #
>/,=
"
7$ # $
>/,>
>/ =
>/ >
>/ =
>/ >
>/>=
>/>>
<<>
<0>
<?>
=>>
= >
=<>
=0>
=?>
0>>
0 >
0<>
00>
@9A
9
5
$! 5
6 5 '
55
&
6
!
# &
&
$
6 !C '
5
$ ! $ #
/
5 !
5 #
'
5
$ ' !
" &
"! /
& !
"!
5 ' ! E
2
8
8
"!
/
'
1
!
5
$
6
&
,
>.
,
<=> F /
!
5
$
" 6 5 !!$ ! )G >>. >> # *
!! " &
6
& 'D &
8/
"! C $
C
5 !
& $2E 2
# !
8
,
"
# '
$
8 % !$55
)E
*C
' 1!
$
'
5
$ ) ?>.,>> F *
!
'!
$ 6! !#"
' 1 6 5 !!$
6 =>. >> # '
$
! 6
! /
'
"!
!
$
5 !!$ &
%
6
!!
5 !!
'
5
!! !
5
5 !!$ !
# ' => # /
! 6 !
& ' 5
E )
5 !! # " &
*
&$
&
5
$
!!$ ) ! ! '
& 6$ <*C
!
! )=> # *
!
!
' "!
# '
>/3?
/> /
!
!
!
! 5
$
!
! '
/
! ! 85
# #
$!
8$ !
5 !
" #"
),,/, 9*/ :
$
5
$
2 ! 6
!6
#"
6
5 !!$
$ /
<
/ >
/>?
/>0
/><
5 !! # " B
/>
/>>
>/3?
>/30
>/3<
>/3
>/3>
>/??
>#
=> #
>> #
>> #
>/?0
>/?<
>/?
>/?>
<<>
<0>
<?>
=>>
= >
=<>
=0>
=?>
0>>
0 >
0<>
00>
@9A
(!
!
6 !C
!
1
!$ !
5$ 5 !
$!
& 5
5 !!$ ! !
&$6
!
1
85 !!
#
6
" 6
&
6! &
,
85
/
5 5 ! #" H
I$!!
B
!# !
$
!$" &
! 6
" ! 5!
" 5
!! $! 6
#! #
: . "5 1
/
!$ !
"
5 8#
$!
&&
' "
"! C
#! 5
# 6 #! 5
/
!
1!
$
& &
! ! 7$
$!/ B
5
&
1
!
55
8 I/
&
!
7$
!
&
' 6(
H
5
9 -9 9,
I$!!
& 5
$!
$
!"
&
$
&
/ I
$!
7$ # $
! ! )&
,
!
1
!
! "
*
6
&
$
! !
' 6 ' "(
9
B
#
& 95-929
!$ C
!
6
)! & 6$
$! &
6 9-959 C
7$
*C
!
&
I ) 2
4 34
==?/ 4
<
,<=,/,?
>
<
4>4>/,<
,0030
/0=
.3<40=
& 6$
= !
6
5
&
$ $!
!#
5 $66 6
5 !!$ !/ I
$! 9
!!
/
' 6' ",(
,>/?
7$
5
! $ 6
&
&
! => /=4 9/
!"
! ! ! &$
&
5
$
$
&
6
:;
7$ # $ /
!
6
:; ! 6
" 6
&
!"
! !C & ! 55 8
!
"5
!!
5 # /
&
$! &
! $
!
!
! #
#
5 !!$ ! & 8
=> # /
& 6$ = ! !
5
$! &
8 $
!$
# >.<>F
# '
7$ # $
5
$ /B
% 6
$
)
!
! !* !
!! " &
' 6 !
/I
$!
' #
5 8
85 !
'
5
$ 6
6
6
&
'! 8 "
! 5 C
5
!! &
!"
!!
$ #
'
6
7$
6
!
! &
5
!!
$ . $#
!
' 1
# ' ! 5 $
/
B
!
6!!
$! &$ !
5 6
!$!
!
&
/
!5
!! '
& 6$ 0/
!5
5
6
!
5
$
!
>
!
!
" '
! 5
!!
$! &
8 $
! !
6
#"
52 / :
#
!
7$ # $
C
& ! #
!
6! !
' # '
5 $
!
!
6
!! !
'
!
!
&$
!6 &
5 6 !! ! 5 !! # /
/
! !
&
>/ >
7$ # $
!
>/ ?
216 !*
>/ 0
>/ <
>/
"
>/ >
>/>
>/>,
>/>?
>/>
>/>0
>/><
>/>>=
.,
>/><
>/>=
>/>
>/>>
<0>
<?>
=>>
= >
=<>
=0>
=?>
0>>
0 >
@9A
)7
78 9:
/>
7$ # $
!
>/3
216 !*
>/?
>/4
>/> >
!
>/0
/> .,
>/> >
>/=
>/>,>
>/<
>/><>
>/,
>/
>/>=>
>/
>/>
<0>
<?>
=>>
= >
=<>
=0>
=?>
0>>
0 >
@9A
.7
78 9:
;
I &
!
6
!$" &
5
"!
& 6$
C
! &5
"
&&
"
$ "
!!
!&
C! 6
& !
"
! ! $
&
/
!
5!
6
5 J /
!
&
!
6
! "/ K
!5
& =. >
! &
!5 " /
!
" &&
#"
!
'
" #6
5
!/
# 66 ! ' ! 5
!
5 $
& /<?
! &
!</
& >/=. /=
! &
! 5 " /
! !$" ' '
!
5 $
&
&
!5 " /
!
B
!C '
6 '
!5
&
2!C
$
6 '
!
C#$C & ' 5 1
6
!
6
&
#
8/B
5 1 #
'
!
&&
!
&
6 $
C
"
&
!
"C!
>>,
6
5
!
5
&
$ #
) -,/3 *
7$
! &
5 1 #
)&
& 6$ = &
8 5 * & >/>>=
216
!! "
'
1 2! &
!5
5
!=(
"
"
$ ! 6 "$
!
#
$!
!
$
$! 6 5 1 6 &
# /
" ' " 6 !
/:
!
&
6
!5
& .,
!
8 ! $
'
& >/04 )!5
!*
!
&
6 !
!5
$ >/3
! 6
!
6
6 ' $ #
.,
! 6
!
C
&
"
!/
"! ! $ !$55
E
&
! K
,/
#
! K
! 7$
85 !
#
$!
5$ " &
"! ! 1 ".
!
"/
!
!
! 1 B C C
"%
B!
5!
'
! & 1 5
6
! !"
! !/ 6
$ %
&
"! !
" 5
/
C# 6
$
# !
"! )!$ &
=>. >>
26*C
&&$!
!
#
5
/
5 !
&
$
&
5
!%
%
!
! #$
! 7$
"
5 !!$
5
!!
# /
!
!
$!
& ! $ $
"! C
! 5 &
&
$! 6 6C
!
&&
"'
$
! 6
5 !!$
5/
5
$!
"!
&&
" !
&' '
$
8 $ * & ?=D
$$!
&&
")
# 6
6 &
$$! ! $ #
8 $
&
'
/03/
' 6 7$
&
'!=(
!&
#
!
60(
$
#
!$ !
I
->/=
$!
!5
! $ $
5
"! '
1 6&
&
&
5
!%
'
'
& # $=
' &
>/04 )5
&
! "#
!(
# !$ #
' ! &
!5
!$ 1
! 6
!*
&
C
/
!
$! 6
6
&
! 5
' 6&
!!
$
#
5 !!$
"
$
$
&
$ (
=
; !
6 ! 8$
!
!$ !
>- ?
!
-<3 #
L! 6
'
$!
$
!(
'#
>>
6 >
&
!$5 &
!!
" ) > 162 !*C # !
5 1 6&
)>/<,*C > !
,
.=
! " ) > 162 *C !
! ! " ) /,, >
!*
5 !
"!
)>/>>= */
>- =>
- >/>? # 2
5 !!$
!!
5 !
#
!5
!
'#
'
!
!
6
!#
#&
>
$!
5
'
1 6&
$!
'/
#$
(
'
#&
%
'
!$ !(
'#
'
'
8 $
&&
# '
6!
!$ &
!6
#"
$ !0(
&
#
(
)
'
!!
!&
&
6
:
#
!!$ C
/
5$
$!
1 !! !
"
1 !!C'
& '! ! &
'!(
*
5
$
" &
$
)>/=
5
"
!&
6
$
" ) $
# !6 &
&
6
5
/
!!
/ I$ '
!$ &
*
!
&$
6* '
# 7$
!
6
!
"
85 !!
$!
"!
+
+,
+,
,
)
'
!5
!!$ #
1 !! !
$!
6
&
;
!
& 6$
$ #
8
6 ! ) /6/ !
5
!
!
$! 6
8
8
6 !
!
&
!
'
&&
!$ !
6 6 " 8
'
5 $
*
! & 7$5
6 !/
&
6
! $
7$
7$
#$
! 5
! )&
7$ # $
6
#
& ' $! 6
&
'
! !
#
! $!!
5
$5$ !
/
6/
6
!
" '
& !
!
$! 6
/
!
5
'
55
8 *
# (
+
+,
+
+,
+
+,
+
+,
+
+,
+
+,
:
#" H
!
!
8
, & !
,
I$!!
/
$
!
6 &
& '&
!5 &
<
!
! &
!"
!
/
!!
5 !
5
:;
!5 5 !
8$ !5 &
!(
!
!
6 &
=D
?D
4<D
,D
&
2! '
&
' 6
5 !
<
'
5
6
$
2! &
! $
8C
!
5
55
8 /
& 6$
4/
>/ >
7$ # $
!
>/ ?
216 !*
>/ 0
>/ <
>/
"
>/ >
>/>?
>/>0
>/><
>/>
>/>>
<0>
<?>
=>>
= >
=<>
=0>
=?>
0>>
0 >
@9A
07
/>
7$ # $
!
>/3
216 !*
>/?
>/4
>/> >
>/0
/> .,
>/> >
>/=
>/>,>
>/<
>/><>
>/,
>/
>/>=>
>/
>/>
<0>
<?>
=>>
= >
=<>
=0>
=?>
0>>
0 >
@9A
!
'
6
$ *
;7
'
&$
5
&
6 /
!
! !!
#
'
) !
& 6$ 3/
& ' &
>>
>>>
3>>
<
2!A
4>>
?>>
0>>
=>>
<>>
,>>
>>
>>
>
>
! #$
I
/=
/4
/?
,
<
! !
8
!5
6 @A
<
! !&
'!(
) *
)9*
<3>
<3>
<3>
<3>
&4
&
6 !C !$ !
#
! /0
<
"
>
!
#
6
=?>
=0
=<?
=,?
/
6
/
$/
'
)9*
2!*
<><
003
??,
>0>
# '
#
6
!&
6
! ,/3
!
!
5 5 " '
&"
5 !!$
5
"/ B
5 !!$
5
!!
# C# &
'
!
>
#
5 !!$
5' ! # $ # /
&
#
!!
C#$ '
5 !!$
5
!!
8
6 !C! '
!$55 ! . #
5 !!$
5&
'
/
!
&&
" &
"! ' !
!!$ C
&
!
$! & ! $ $
"!
1
$! 6 6' !
! /:
5
"' "
&&
"& #
6
/ ! 5
& 6$
>/
"!
&&
<
/>
>/3
>/?
:;
>/4
>
<
:
5
!
$
&
#
BB
"!
#
&
'
&
&&
" !
!!$ C'
"! !
5 5 " $!
$ ' ! #
?=D /
!
5
,
<
5
) *
!
) *
/=
/4
/?
&
/
" ' " !
1 6
& 6$ 4 '
$
!
$ %
* !
&
'!
&
6
5 !
/
# & C' $ #
85 !
6
!
55 8
& !
' !
# !
'
! " 6 !
!
!
6 #
# !
!
! /
5
( '
!
!
"!
5
# )&
C8
6 C M *N
!
"%
&&
&
$55
5
$
!6
" 85 !!
!
&
7$ # $
I
I
I
I
1&
:;
& !
' 4>D C
5
!6 )
! &
"!
5 !
6
$! &
8 $
&
'! 8 " !
C !
"
5 8/
!$ 6 !
1
!! ! 5 $
/ # $! "
"
&&
" #$
6
$ #
&
!
! ! !
#
8
! !!
'
) 8
!
5
$ &
5 !
/
!6
<3>
<3>
<3>
<3>
&&
")
)
2!*
<><
003
??,
>0>
L )9*
=?>
=0
=<?
=,?
!*
= /<
I
I
I
I
,
<
5
I
I
I
I
,
<
5
! '
>
>9
) !8 *# /
# #"
&
7$ # $ C#$
'
4 # /
5 ) *
/ =
/,
/,
/,=
=/
<3>
<3>
<3>
<3>
&&
5 ) *
/>?
/
/>=
/ =
</<
6
5 $ &
!' "" $
)
,4<
0>3
43=
3<0
)9*
=4,
==,
=<>
=,
L
")
<3>
<3>
<3>
<3>
&&
")
!*
!*
&&
"C#$ &
!5 #
)' 6
!
0D
6
? /3
)
,,>
=,
0?>
? =
L )9*
=0,
=<<
=,>
= ?
2!*
2!*
?4/=
6 1 2!
&&
$! < # !* !
$ <.= 9
5 $
! 5 !! #
PL
.9'
:
! 7$
6.
&!
! $#
7$
5
&
!
&!
&
' 6(
!&
#
5
5 !
. 1
/
5$
85 !!
"
:
$
"
:
5 '
&
9 C
8 6 $ ! ! 5 !! #
!
8$ ! & "
# !/
!
#
&
'
! '
&
" $!
!
$! 6 55 5
'
& $ C !5
" &
5 8
8 6 $ !
# !
$! 6
7$
!5 !
&
6
5$
6
&
' 6' "/
!
!
B
5
!
5
! 6
! ! 5 !! #
6!
/
" 5 #
! 5 !! #
'
$#
7$
/ I
$! 6
"
! $ # $! /
$
/
#
!
&
&
&$6
6 !/
"
&&
&
"
$
$
6!
5
4
&
!"
5
!!
& !
!
C&
5 #
&8
$
!
$
! $! 6 9
! $!!
#
/
&
C
C
&
$
HC
" &
"5 5
8$
5
&
1
&
>
)9*
)# *
6
5
#
&
0<4/,
/
>/,<<
,/==3>04
/< ?3?
/<3> 3
>/=?, ,
>/ ,,, 3
>/,<403
>/> 4,<0
/==<?3?
>/044, ,
,/4>>= =
>/? 304
>/0, 34
/,,3<==
>/> 3003
</ ><
,/?==>=
>/ = ,?4
>/ ,,<>?
>/,3404,
>/ >>,04
>/> ?<?=
>/4,>4 ?
>/ 0><
=/=3 4>
/>>>=
/, =3,
4/,,<>,0
>/> >03
>/ =
>/ =
>/>?
>/>?
>/4<
>/4<
>
>
>
>
>/>>< > >/>> ,4< >/> ,043

/3>4 <0 0/,>?
</> 43 ,
>
>
> >/>>>?3< ............G >/> ><3 #

> / 3<?= ............G >/ ? 0<,
& )# *
5 )# *
4/0?
/>
= >/? 0 =
<0 ,/3 3=
,4/4?=,
4/=
<
,4
3>/0
<0/><
>/>
,,/,
/34
.>/ =
/> < 00 >/3? ,4?
= /0
?>/30
>/=00
,></
4,/?
>/ ?
">
"
"#
" 2#
<
, /3
,</33
>/>00
>/3 4<4 /<? 0,4

>/0 4=?3 />?0>
3/=?>?0
/, 3, 0
/, < ? >/<34 3,
/ >0 <4 >/=>30<3
>/=3?43 / ?4 ,,
>/><==?0 >/> 3?>0
>/?333,,
>
>
>
>
>/>?,
H6
H
<4, 9
=> #
>/4?0
,2
>/?>>=
,2
>/>,
>/>,
/>>? <
/=
/=
,#
/> ?,
29
OI
OI
" &
55 ! !
!
%
!&
'
7$ # $
$# !
!
'!,(
"! ! !$55 !
8 %
#"
#
:;
6 6
&
&
$
#"
6/
'
!"
"! 6 ! 5'
! !/
5 !
OI
! 5
$
%
$
#
$
$&
$
$ %
$
$
$
%
$
%
$
$ %
$ %
$
$ %
! 5
$
$ %
$ %
7$ # $
&!
$
! !
$
!
&
!/
' 6(
# ! 5 &
&
!5
! ! & 5! $ !
"!
&
!5 !
"5
!C'
!
6!5
!
! /
>
#
& #! #
!
!5
6" #! #
! 5
!
/
"&
OI
# !
7$
5 ! 6
$ 6
&
! # 6
! 5 &"
&
!$ !(
C#$
"
5 !
5 "!
6/
!$ !(
6 &
85
$
&
85 !!
&
#
#
&
!(
5
!$ !
!
#
6 $5! & !
6 6# /
!
'!
OI
85 !!
!5 !
9,
# '
!(
$! "C6 $5 6
7$ # $
! )5
$! " 9
9,Q*
L H
!
! $
6 !
7$
PL
! &
&
"
&
!!
1 !! %(
%
+
+
+
+
+,
$
(
# &
&&
" & #
!"!
& 7$
5 !
+
+,
+
+,
+
+,
+
+,
+
+,
+
+,
B
5 5
5 !
5
5
$ (
'
&&
" !
$5
&
6 6
!
:
$! &
,>/?4
3/?>
4/ <
, / <
/ =
3/ =
<
I
. / ?=
4/,<<
3/ 4<
/3 <
4/>3
=/ ,
.
.
.,
.,
.
.
<
/4?3
.=/0>
. /,?
/>==
/=?4
/ 34
.=
.=
.=
.=
.=
.=
. / 4
/4 =
4/0<=
.,/=30
. /?=
. / ,
.?
.?
.3
.3
.?
.?
:
5 $
,
: ; #"
/
$ &
&&
#
&
&&$!
85 !!
#"
0
&&
6'
I ) 2
!(
,>/?
4 34
==?/ 4
<
,<=,/,?
>
<
4>4>/,<
,0030
/0=
.3<40=
7$ # $
# "
!(
I$!
&
'
I
$!
& 'C$! 6
85 !!
&
&
6
&
5
'
5 !!$ !
' (
!
L! 6
5 5
$ &
5" &
5$
'
'
6
!!
'
! '
55
8 /
5 !
5 &
:
7$
!
!
7$
6 6
B
! 5 !
5 5
55
"
# $
! $
5$ 6
!/
&&
)
)
)
)
)
)
85
7$
! !
#"
$!
*2 )%* ,Q ,Q
Q #Q
*2 )%* - ).
Q . ,Q ,*Q
Q #Q
,*2 )%* - ).,Q
Q . ,Q ,*Q
Q #Q
<*2 )%* - )
Q + ,Q ,*Q
Q #Q
=*2 )%* Q Q
Q #Q
*2 )%* - )
Q
Q + ,Q ,Q ,*Q #Q
Q 2) 5Q)
+ + ,+ <+ =+ 0**
7$
! !
#"
$!
0 - ,0>
" - 2) + + ,+ <+ =+ 0*
" - 2) + + ,+ <+ =+ 0*
", - ,2) + + ,+ <+ =+ 0*
"< - <2) + + ,+ <+ =+ 0*
"= - =2) + + ,+ <+ =+ 0*
"0 - 02) + + ,+ <+ =+ 0*
9 - >/34<Q 85) / =+3 <,/02 .4/<3 Q ) *+</>40Q >R).,*Q .4/ 0 Q >R).?*Q R *
9, - 85) ,/ <?.=0,3/=2 . />44Q ) *.=/<<Q >R).<*Q + / =Q >R).4*Q R +<3 4>2 R *
9 - 9 Q9,
< - 4>4>/,<
- =>
# - 4 34
# - < 3
#, - >
#< - ,0030
- => /=4
- ,>/?
- ==?/ 4
, - ,<=,/,?
$!
"
&&
6
! &
< - <Q 85).#<2?/, Q) 2

. 2 **
= - /0=
- Q 85).# 2?/, Q) 2
. 2 **
- Q 85).# 2?/, Q) 2
. 2 **
, - ,Q 85).#,2?/, Q) 2
. 2 **
- ) <Q R Q" Q",Q) .)"<Q"=2) R Q9 Q",R,Q" ****2))
#= - .3<40=
= - =Q 85).#=2?/, Q) 2
. 2 **
- . / 4 Q >R).?*
- /4 =Q >R).?*
, - 4/0<=Q >R).3*
< - .,/=30Q >R).3*
= - . /?= Q >R).?*
0 - . / , Q >R).?*
0 - / 34Q >R).=*
, - ) =Q Q" Q) .)"<Q" 2)9,Q",Q" ****2) + ,Q"<2",+
&& - </ Q >R).?*
&& - =/04Q >R).?*
- 3?>
- >/>>>=
- Q))) R *R>/=*Q
Q>/>>>>?, Q 2 2" 2 &&
# - >/<,
, - Q))) ,R *R>/=*Q
Q>/>>>>?, Q 2 2" 2 &&
, - ),2) ,R **Q)) ,2
) ,**. *
- ),2)
R **Q))
2
)
**. *
- =<>>>
, - .<>0>>
- ,>/?4
- 3/?
, - 4/ <
< -, / <
=- / =
0 - 3/ =
I - . / ?=Q >R). *
I - 4/,,<Q >R). *
I, - 3/ 4<Q >R).,*
I< - /3 <Q >R).,*
I= - 4/>3 Q >R). *
I0 - =/ ,Q >R). *
- /4?3Q >R).=*
- .=/0> Q >R).=*
, - . /,? Q >R).=*
< - />==Q >R).=*
= - /=?4Q >R).=*
50 - 0+I0Q + 0Q R + 0Q R,
5 - +I Q + Q R + Q R,
5 - +I Q + Q R + Q R,
5, - ,+I,Q + ,Q R + ,Q R,
5< - <+I<Q + <Q R + <Q R,
5= - =+I=Q + =Q R + =Q R,
5 - " Q 5 +" Q 5 +",Q 5,+"<Q 5<+"=Q 5=+"0Q
+ ,Q"<2",+
Q R>/=Q",R>/=+
Q R>/=Q",R>/=+
*R>/=
*R>/=
50
Q Q"<*
Q Q"<*R,*
!
=D
?D
4<D
,D
5 !
&(
<
&
&
!$ !
9
5
2! ) # $
2!
8 5 6 !/
! &
&
<3> 9/
%
@A
>
>/>,>><
>/><==>3
>/>0>0 <
>/>4=>
>/>3>>00
>/ >=300
>/
0=
>/ ,==>=
>/ = =
/,=>=?
/,004 4
/,? =4
/,3=>>
/< >?30
/< =, 3
/<<>,
/<==?0
/<4 >4
/<?0= 0
/=
9
@# . A
>/> >,0<
>/>>3< ,
>/>>3 >=
>/>>??,=
>/>>?0
>/>>?,4
>/>>? <
>/>>43 =
>/>>44,=
>/>>4= ?
/0, .><
/=? .><
/== .><
/= .><
/<? .><
/<0 .><
/<, .><
/< .><
/,? .><
/,4 .><
/,= .><
2!A
?>>
?>,/>??
?>,/033
?>,/3 3
?>,/???
?>,/0 <
?>,/ ,?
?> /<=<
?> /40,
?>>/?
=,>/ <4
= ?/?,
= 4/0
= 0/0
= =/<4?
= </=,=
= ,/0,
= /40
= /3,
= / =
= >/000
9,
>/>>0 33
>/>>0=<4
>/>>00,3
>/>>04
>/>>043<
>/>>0?03
>/>>03<4
>/>>4> 0
>/>>4>3
>/>>4 4
>/> 4 ?
>/> 4 3
>/> 4<<
>/> 4=00
>/> 44>0
>/> 4? ,
>/> 43,0
>/> ?><=
>/> ? =
>/> ? ,0
>/> ?,>?
2!A
30>
3< / ,<4
3,=/,,<=
3,>/043=
3 0/3,3
3 ,/=03?
3 >/<0<=
3 4/043?
3 =/0 3?
3 ,/< ,=
?,3/4 =?
?,3/ 33
?,?/0 04
?,?/ >>=
?,4/4 33
?,4/,,,
?,0/3=>=
?,0/=? 4
?,0/ ,>
?,=/3<><
?,=/03>
,
@ 2!A
???>
?? 3/??
?? ,/<>
?433/?34
?4??/=3<
?444/3=?
?404/04
?4=4/3<?
?4=>/,?=
?4< /?0<
4343/0<
434=/>=
434 /
4304/?>
430</ <=
430 />03
43=?/
43==/ 4
43= /===
43=>/, 0
43<?/<>
9
@# . A
#
0/=, .>=
0/ 4 .>=
0/>= .>=
=/3< .>=
=/?< .>=
=/4= .>=
=/00 .>=
=/=0 .>=
=/<3 .>=
=/<> .>=
4/
.>0
4/>= .>0
0/33 .>0
0/3< .>0
0/?? .>0
0/?< .>0
0/43 .>0
0/4= .>0
0/4 .>0
0/0? .>0
0/0= .>0
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
<
@ 2!A
=
@ 2!A
>
?/40=,
</00=<4
3/, >=,
,,/>0>3=
,0/<,> ,
,3/=,==
< /, > =
<</,?>
<0/=?0=
>/ ?<
>/?4>
/,4,,
/433=
/ 4>
/004
,/><3=
,/< 4,
,/4033
</>=30
</,>33
@ 216!A
>/ <,?03
>/>=> >4
>/>,30?
>/>,,?00
>/>,> 3
>/> 44 ?
>/> =?,
>/> <<0<
>/> ,0<
>/> 3,<
>/> <,=?
>/> , 30
>/>
3,
>/> ,,?
>/> >,?3
>/>>3=?=
>/>>??>0
>/>>?>==
>/>>4,,
>/>>04,=
>/>>0 ,,
>
=/044
>/3003
=/,3 <
3/ 4 40
, /?>0
,0/,34 3
,3/?00 <
< /0 4 ?
<=/44<?
,3>/>,4,
,3 />,3=
,3,/4= 4
,3=/ 33=
,30/43 ,
,3?/ , ?
,33/<
<>>/0==0
<> /?,44
<> /?>4<
<>,/0<<
@9A
<3>
<3 /3,0,
<3 /0,4,
<3,/ =<<
<3,/?>43
<3</,0<=
<3</3,3,
<3=/= ?
<3=/33,=
<30/==0=
=40/0>=4
=44/>==0
=44/<<>=
=44/40=,
=4?/
?
=4?/< ,,
=4?/4
=4?/3?3,
=43/ =<,
=43/<4 0
=43/0=3
0
@ 2!A
,0>
,0>
,0>
,0>
,0>
,0>
,0>
,0>
,0>
,0>
,0>
,0>
,0>
,0>
,0>
,0>
,0>
,0>
,0>
,0>
,0>
,
@
,
216!A
>/> ?=? </ 33?<< >/3,?<,?
>/>>=< 4 /=><?
>/=>4>0
>/>> =4 / ,000= >/,<?30
=/ < .><
/>4 3? >/ =4=?
.>/>> >,
/30,34? >/
>?
.>/>> ,?? /?? 3?0 >/,,00?3
.>/>>,0 , /? >330 >/< <?0
.>/>><4,, /44=,03 >/<4<,44
.>/>>==0< /4<40? >/= <=34
.>/>>0<4= /4 ,3>< >/===<
.>/>>3 =0 /<??> < >/4=,=
.>/>>?== /< 4,04 >/4 <043
.>/>>43,< /,4 000 >/03?= ,
.>/>>4<>4 /, < >, >/04= ,<
.>/>>0? ? / 0? =, >/0<? =?
.>/>>0, = / ?=<? >/0 <>0?
.>/>>=? < / 0?<< >/=330 ,
.>/>>=,<? / 4?0, >/=4<?>
.>/>><??0 />00?<0 >/=<30<4
.>/>><=>, /> ?>, >/= 4? 4
.>/>>< 43 >/3?< 0 >/=>?0>=
=1 7
"
"
>/
>/
>/
>/
>/
>/
>/
>/
>/
>/
>/
>/
>/
>/
>/
>/
>/
>/
>/
>/
>/ =
=>0=
=>?,=
=>300
= >=3
=
?
= 43
= >3
=
=
,0,?4
,0,>3
,0 <,
,0 ?4
,0 =
,0>4<
,0> <
,=344
,=3,
,=?3<
,=?0,
",
>/>?
>/>4?0<
>/>4? ?
>/>44??0
>/>440
>/>44,?4
>/>44 4<
>/>403?=
>/>40?<?
>/>404>,
>/>4<?<
>/>4<? 0
>/>4<43<
>/>4<44=
>/>4<4==
>/>4<4,4
>/>4<4
>/>4<4><
>/>4<0??
>/>4<04=
>/>4<00<
>/4<
>/4,44=
>/4,4> 0
>/4,0<<
>/4,=30
>/4,== ?
>/4,=>3?
>/4,<4
>/4,<< =
>/4,<>?3
>/4
>,
>/4 ><4
>/4 >3 <
>/4 >?>
>/4 >044
>/4 >=4,
>/4 ><4
>/4 >,4=
>/4 > ?,
>/4 > >4
>/4 > <,
>/=<<==,
>/4,=0,
>/44 =0
>/43=40
>/? >3
>/? 0>
>/?, <>
>/?,4?00
>/?< 443
>/?<= ,,
>/?44??
>/??0>40
>/?3,,=3
>/?334 ,
>/3>03,=
>/3 , >
>/3 3,34
>/3 ==>4
>/3, =>?
>/3,0=<3
>/3<>?=3
5
@2
9A
, />=?0=
, />33<<
, / ,3
, / 0<
, / ,4<4
, / <?<,
, / =30
, / 4>4
, / 4340
, / 3>,?
, /?>0,0
, /? 0??
, /? =?3
, /?,,=
, /?< ?3
, /?<?30
, /?==4=
, /?0 ?
, /?0?=,
, /?4,0=
, /?443=
,
>/3<=? =
>/3?, 03
>/33 34=
>/33?,<3
>/3304=0
>/33 = ,
>/3??4
>/3?=,
>/3? 4?
>/3?>>
>/30<>?<
>/3000=,
>/30?3
>/34>?00
>/34,>0?
>/34<30,
>/340? ,
>/34?0<=
>/3?><
>/3? 3>0
>/3?, 03
& 1) $
,>
"<
>
>/>> =0?
>/>> >0,
>/>> <=<
>/>> 403
>/>>,>=,
>/>>,, =
>/>>,==
>/>>,4 =
>/>>,3
>/> >4
>/> >444
>/> >? =
>/> >?00
>/> >3
>/> >3<3
>/> >3?=
>/> >
>/> >==
>/> >?
>/>
>0
"=
>
>/>> ,
>/>> 4=,
>/>>
=
>/>> <<,
>/>> 4<3
>/>>,>=
>/>>,,<<
>/>>,=44
>/>>,?<<
>/>,<40,
>/>,<3=<
>/>,= 4
>/>,= ==
>/>,=<>?
>/>,==,0
>/>,=0=3
>/>,=444
>/>,=?3
>/>,=3?,
>/>,0>0
"0
>/>,
>/>,>>43
>/>,> >=
>/>,> ?
>/>,> <4
>/>,> 0=
>/>,> ?,
>/>,> >
>/>,> =
>/>,> ,
>/>, >?0
>/>, >34
>/>, >4
>/>,
=
>/>,
=
>/>, ,
>/>, <
>/>, <4
>/>, =,
>/>, =3
>/>, 0<
%
@A
/=
/=
/=>>
/=>> =
/=>><4=
/=>>? ,
/=> , 3
/=> >4?
/=>, 4
/=><3 0
,/><==4,
,/>0 =<3
,/>4?>3
,/>3= <
,/ ,>=
,/ ?<,,
,/ <4<<
,/ 0,,?3
,/ 43<=4
,/ 3?3=3
,/
9
@# . A
>/> >,0<
>/> >,0<
>/> >,0<
>/> >,0
>/> >,0
>/> >,=4
>/> >,=
>/> >,<=
>/> >,,=
>/> >, 3
=/>> .><
</3= .><
</3 .><
</?0 .><
</? .><
</43 .><
</40 .><
</4, .><
</4 .><
</0? .><
</0? .><
2!A
= >/000
= >/000
= >/0=
= >/0,
= >/0
= >/==
= >/<?
= >/,40
= >/ 0
= 3/344
<4/,0
<0/=<0
<=/44,
<=/><,
<</,=0
<,/? 0
<,/
< /4=,
< /,,,
< /?4<
< /?=
9,
>/>>0 33
>/>>0 33
>/>>0,
>/>>0,
>/>>0,
>/>>0,>
>/>>0,>
>/>>0,><
>/>>0,>4
>/>>0,
>/> >30
>/>
44
>/>
==
>/> , 3
>/> ,3?
>/> <=,
>/> = =
>/> =0
>/> 0>=
>/> 0=
>/> 0=,
@ 2!A
?,=/03>
?,=/03>
?,=/4> =
?,=/4
?,=/4<3
?,=/43
?,=/?=<
?,=/3<?<
?,0/>3
?,0/,> <
?= / =>3
?=>/34 ,
?=>/4>03
?=>/<==
?=>/ 4
?=>/> 34
?<3/? 3
?<3/0=3,
?<3/= <
?<3/,= 4
?<3/,<,0
,
<
=
0
@ 2!A
@ 2!A
@ 2!A
@9A
@ 2!A
43<?/<>
</,>33 <>,/0<<
<3>
,0>
43<?/<>
</,>33 <>,/0<<
<3>
,0>
43<?/<
</ 34= <>,/0<== <3>/>> ?
,0>
43<?/< 0
</ 4?3 <>,/0<4? <3>/>><=
,0>
43<?/<<4
</ =>3 <>,/0= , <3>/>>?0
,0>
43<?/<4?
</ >?3 <>,/0=0= <3>/> <4
,0>
43<?/= 0
</ <0 <>,/00<, <3>/> ,?
,0>
43<?/=34
</>= 0 <>,/040 <3>/>,40
,0>
43<?/4>,
,/3 <>,/03,0 <3>/>=?
,0>
43<?/?0
,/0340 <>,/4 >, <3>/>?3
,0>
4<<?/<4, >?/4<3 00 /,??3 ==3/<<,0
,0>
4<<0/>>? >3/> 44 00 /<? , ==3/0330
,0>
4<<,/004 >3/ 3,
00,/= ==3/3< <
,0>
4<< /<=
>3/=<<? 00</=> 4 =0>/ 4
,0>
4<,3/,0, >3/4? ? 00=/< 4 =0>/,??=
,0>
4<,4/4
>3/34>, 000/ =<4 =0>/==?0
,0>
4<,=/?43
>/ ?>? 000/3033 =0>/4<3
,0>
4<,</<?,
>/,<>4 004/=?? =0>/?3,0
,0>
4<,,/ >,
>/<?40 00?/ =<? =0 /> 0
,0>
4<, /?><
>/0<?, 00?/44< =0 / 4>0
,0>
4<, /4,<
>/0=0< 00?/?>= =0 / 443
,0>
9
@# . A
#
0/=, .>=
0/=, .>=
0/=, .>=
0/=, .>=
0/=, .>=
0/=, .>=
0/= .>=
0/= .>=
0/= .>=
0/= .>=
/>0 .>=
/>= .>=
/>< .>=
/>< .>=
/>, .>=
/>, .>=
/> .>=
/> .>=
/> .>=
/> .>=
/> .>=
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
@ 216!A
>/>> = 3
>/>> = 3
>/>> =
>/>> =
>/>> =
>/>> = =
>/>> = ?
>/>> =,<
>/>> =<
>/>> ===
>/>>4<=3
>/>>0? 4
>/>>0 >,
>/>>=0 4
>/>>=>0
>/>><0
>/>>< ,
>/>>,4<<
>/>>,,3=
>/>>,>
>/>>,>>
,
@ 216!A
.>/> <,,0
.>/> <,,0
.>/> <,,4
.>/> <,,?
.>/> <,<
.>/> <,<
.>/> <,<0
.>/> <,=
.>/> <,0
.>/> <,4<
.>/>>=,,=
.>/>><??4
.>/>><<=0
.>/>><><<
.>/>>,0=
.>/>>,,,3
.>/>> 3?0
.>/>> 4 0
.>/>> <00
.>/>> 3
.>/>> ?,
,
>/<<0034
>/<<0034
>/<<0433
>/<<03=,
>/<<4 ?,
>/<<4= 3
>/<<?><?
>/<<?? ?
>/<=>>>
>/<= 40?
/> ,=<4
>/34??,
>/3,,3=
>/???34<
>/?<,3?4
>/?>0==<
>/40
0
>/4 0,3?
>/03 ? ,
>/0= 4<=
>/0=><3<
>/?00 ,4
>/?00 ,4
>/?00 00
>/?00 >3
>/?00 4,
>/?00,4
>/?00= =
>/?004,
>/?04>=4
>/?04=<<
>/0>?? 4
>/=? 303
>/==03,<
>/=,>40,
>/=><=><
>/<? =3<
>/<=0= 4
>/<,=<3
>/< =>34
>/,3 <>
>/,3>00
"
"
>/
>/
>/
>/
>/
>/
>/
>/
>/
>/
>/
>/
>/
>/
>/
>/
>/
>/
>/
>/
>/
,=?0
,=?0
,=?0
,=?=3
,=?=0
,=?=
,=?<0
,=?,4
,=? ,
,=?>,
0? <
044
04
004=
00,
0=34
0==?
0= ?
0=>
0<4
0<4
",
>/>4<00<
>/>4<00<
>/>4<00=
>/>4<004
>/>4<003
>/>4<04,
>/>4<043
>/>4<0?4
>/>4<4
>/>4<4
>/>434 0
>/>434 0
>/>434>4
>/>4303?
>/>430?3
>/>430?,
>/>4304=
>/>43003
>/>4300<
>/>430=?
>/>430=?
>/4 > <

>/4 > <
>/4 > <
>/4 > <,
>/4 > <0
>/4 > <3
>/4 > ==
>/4 > 0
>/4 > 4<
>/4 > 3
>/0340><
>/034= 0
>/034<,
>/034,=,
>/034 4?
>/034 3
>/034 =,
>/034 >,
>/034>=4
>/034>>4
>/034>>0
>/3?03<=
>/3?03<=
>/3?03,3
>/3?03,
>/3?03 4
>/3?0?3?
>/3?0?0?
>/3?0? ,
>/3?04==
>/3?00=,
>/3,0<0=
>/3< <<=
>/3<0 3,
>/3=>33
>/3===
>/3=3 =<
>/30,,>
>/300=>
>/303<?
>/34 4?
>/34 ??
5
@2
9A
, / ,?=4
, / ,?=4
, / ,?0
, / ,?0=
, / ,?4
, / ,??
, / ,?30
, / ,3 3
, / ,3=,
, / <>><
,,/4>04
,,/4 ,,?
,,/4 34
,,/4 =4,
,,/4, ,3
,,/4,=?=
,,/4<>?<
,,/4<<0
,,/4<?
,,/4= ?3
,,/4= >
,
>/3=,,
>/3=,,
>/3=,,>?
>/3=,,><
>/3=, 3?
>/3=, ??
>/3=, 4,
>/3=, =
>/3=, 3
>/3=, 4
>/340 ,
>/34?>=
>/3433 <
>/3? 4
>/3?,<,,
>/3?<?
>/3?0,40
>/3?4=?
>/3??03?
>/3?33,<
>/3?334
1) #
"<
>/>
>0
>/>
>0
>/>
>=
>/>
><
>/>
>
>/> >34
>/> >3
>/> >?,
>/> >4
>/> >=
>/> > ?=
>/> > ,
>/> > <
>/> > 00
>/> > 3
>/> >,>3
>/> >,,
>/> >,<0
>/> >,0
>/> >,44
>/> >,4?
"=
>/>,0>0,
>/>,0>0,
>/>,0>0,
>/>,0>0<
>/>,0>0<
>/>,0>0<
>/>,0>0=
>/>,0>00
>/>,0>0?
>/>,0>4
>/>0 3<<
>/>0 >=3
>/>0 0?
>/>0 4
>/>0 ,03
>/>0 <<0
>/>0 =,
>/>0 =34
>/>0 0=4
>/>0 4
>/>0 4 <
"0
>/>, 0<
>/>, 0<
>/>, 0<
>/>, 0<
>/>, 0<
>/>, 0<
>/>, 0<
>/>, 0<
>/>, 0<
>/>, 0<
>/>,,4 4
>/>,,4 <
>/>,,4,
>/>,,4,0
>/>,,4<
>/>,,4<4
>/>,,4=
>/>,,4=0
>/>,,4=3
>/>,,40,
>/>,,40<
%
@A
,/
,/
,/ >>
,/ >> =
,/ >><4=
,/ >>? ,
,/ > , 3
,/ > >4?
,/ >, 4
,/ ><3 0
</? =><
</?<< <
</?0>0=
</??>340
</?3? ?3
</3 =<0
</3, ?<,
</3=>,43
</30? >3
</3?0>4
=
9
@# . A
>/> >,0<
>/> >,0<
>/> >,0<
>/> >,0,
>/> >,0
>/> >,=?
>/> >,=<
>/> >,<?
>/> >,,3
>/> >, 0
?/,, .><
?/ < .><
?/ 4 .><
?/>3 .><
?/>, .><
4/3? .><
4/3, .><
4/?? .><
4/?< .><
4/?> .><
4/4? .><
2!A
< /?=
< /?=
< /?<
< /? <
< /433
< /40
< /4>0
< /0 ,
< /<34
< /,>3
> 0/30?
> 0/>33
> =/< 0
> </0<,
> </><?
> ,/=>
> /330
> /=,
> / ><
> /4
> /< 3
9,
>/>>0 33
>/>>0 33
>/>>0,
>/>>0,
>/>>0,
>/>>0,>
>/>>0,>
>/>>0,>,
>/>>0,>0
>/>>0,>3
>/> 4 0
>/> 4,,0
>/> 4,3<
>/> 4<0
>/> 4=
>/> 4=0
>/> 40>,
>/> 40<<
>/> 40?
>/> 44 0
>/> 44,?
@ 2!A
?<3/,<,0
?<3/,<,0
?<3/,= 3
?<3/,00?
?<3/,?40
?<3/< ??
?<3/<0==
?<3/=,=4
?<3/0<>3
?<3/43?0
?=0/00 =
?=0/< 4
?=0/ ,3
?=0/>><,
?==/?,<
?==/0403
?==/=, 4
?==/,34=
?==/ 4,<
?==/ =??
?==/>44
,
<
=
0
@ 2!A
@ 2!A
@ 2!A
@9A
@ 2!A
4<, /4,<
>/0=0< 00?/?>=
<3>
,0>
4<, /4,<
>/0=0< 00?/?>=
<3>
,0>
4<, /4,3
>/0<4 00?/?>0? <3>/>> =
,0>
4<, /4<?
>/0,,, 00?/?>3= <3>/>>,3
,0>
4<, /40
>/0 = 00?/? ,= <3>/>>4,
,0>
4<, /4?
>/=? , 00?/? 3< <3>/> =
,0>
4<, /?>3
>/=,<= 00?/? ?< <3>/> >,
,0>
4<, /?=
>/<0<, 00?/?< ? <3>/>,
,0>
4<, /3 4
>/,=3 00?/?0
<3>/><30
,0>
4<, /> ,
>/ > < 00?/?3 4 <3>/>40
,0>
4> ,/3
>,/,,?= ?40/,4 =<0/=>>,
,0>
4> /<= >,/=? ? ?44/<?,? =<0/44><
,0>
4> 3/=>, >,/440 ?4?/,0>= =<0/3?,
,0>
4> 4/, >,/33=? ?43/,= , =<4/ ,4
,0>
4> =/=3?
></ 00 ??>/ ? =<4/<>3,
,0>
4> </>,
></, , ??>/? 0
=<4/=?
,0>
4> /=?? ></<0?, ?? /<4 =<4/4,4,
,0>
4> / =0 ></0> = ?? />4>0 =<4/?? ,
,0>
4> >/> ? ></4 00 ?? /0 4 =<?/> 0
,0>
4>>?/?3= ></?<
??,/ , 4 =<?/ ,3
,0>
4>>?/>?3
></3 , ??,/<3< =<?/ 03
,0>
9
@# . A
#
0/=, .>=
0/=, .>=
0/=, .>=
0/=, .>=
0/=, .>=
0/=, .>=
0/=, .>=
0/= .>=
0/= .>=
0/= .>=
/<< .>=
/<, .>=
/< .>=
/< .>=
/< .>=
/<> .>=
/<> .>=
/,3 .>=
/,3 .>=
/,? .>=
/,? .>=
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
@ 216!A
>/>> 4<3
>/>> 4<3
>/>> 4=
>/>> 4=
>/>> 4=
>/>> 4==
>/>> 4=?
>/>> 40,
>/>> 44
>/>> 4?,
>/>>0 =0
>/>>=03
>/>>= <
>/>><4 4
>/>><, =
>/>>,3=
>/>>,0><
>/>>, ?
>/>> 3?,
>/>> 4>=
>/>> = ,
,
@ 216!A
.>/>
=3
.>/>
=3
.>/>
=3
.>/>
=3
.>/>
0
.>/>
0
.>/>
0,
.>/>
0=
.>/>
03
.>/>
4<
.>/>><4=<
.>/>><, 3
.>/>>,33
.>/>>,0>
.>/>>, 34
.>/>>,> =
.>/>> 4=
.>/>> =>?
.>/>> ?
.>/>> >4
.>/>> 3,
,
>/<0<>=3
>/<0<>=3
>/<0< <?
>/<0< ?
>/<0<<?
>/<0<4?,
>/<0= ,0
>/<0=3 =
>/<003,0
>/<0?<4
>/3><44,
>/?0, 4
>/? ?0
>/4?4><?
>/4= 34<
>/4 3?=3
>/0?40<
>/0=0 40
>/0 =4 0
>/=3=300
>/=4=0 <
=# 7
>/? 3>
>/? 3>
>/? 3> 0
>/? 3>=
>/? 3>?4
>/? 3 <
>/? 3 =
>/? 3,<?
>/? 3=,,
>/? 3?
>/0 , ?0
>/=?==?,
>/=0 <
>/=,<=?4
>/= 4,3
>/<?3=>,
>/<04?<
>/<<04 ,
>/< 0 3
>/<>0><
>/,3 3
"
"
>/ 0<4
>/ 0<4
>/ 0<03
>/ 0<0?
>/ 0<00
>/ 0<0
>/ 0<=4
>/ 0<=
>/ 0<,?
>/ 0<
>/ >> 3
>/ >> =0
>/ >> >0
>/ >>>=
>/ >>>>4
>/>33304
>/>333,
>/>33?34
>/>33?00
>/>33?,4
>/>33? 3
>/>430=?
>/>430=?
>/>430=3
>/>4300
>/>4300
>/>4300=
>/>4304
>/>43044
>/>430?4
>/>434>
>/>?,=33
>/>?,=3,
>/>?,=?3
>/>?,=?<
>/>?,=?
>/>?,=40
>/>?,=4
>/>?,=03
>/>?,=00
>/>?,=0,
>/>?,=0
>/034>>=
>/034>>=
>/034>>=
>/034>>0
>/034>>?
>/034>
>/034> =
>/034>
>/034> 3
>/034><
>/0?=<<<
>/0?=,=
>/0?= 43
>/0?= 34
>/0?= ,,
>/0?=>4<
>/0?=>
>/0?<34
>/0?<3 <
>/0?<??
>/0?<?=<
>/3?=3,
>/3?=3,
>/3?=3 0
>/3?=3 ?
>/3?=3>0
>/3?=??3
>/3?=?0
>/3?=?
>/3?=40
>/3?=00?
>/3<3,=3
>/3=,0
>/3=4> 4
>/30>33?
>/30< ,<
>/304>4=
>/303?,
>/34 < 0
>/34<?,<
>/344>3=
>/34?=?0
5
@2
9A
,,/> ,>,
,,/> ,>,
,,/> ,>0
,,/> ,
,,/> , 4
,,/> , 4
,,/> ,<
,,/> ,0=
,,/> ,33
,,/> <=
,</<<?=3
,</<=0 3
,</<0 ,=
,</<03
,</<4<=
,</<43,3
,</<?,?3
,</<??><
,</<3 ?0
,</<3=,3
,</<344
,
>/3=03?3
>/3=03?3
>/3=03?4
>/3=03?=
>/3=03?
>/3=0340
>/3=030?
>/3=03=0
>/3=03,?
>/3=03
>/34=43
>/344?0
>/343= ?
>/3? <=
>/3? 300
>/3?<,?
>/3?=4>0
>/3?03<<
>/3??
>/3?3 4?
>/3?3??3
",
) $
"<
>/> >,4?
>/> >,4?
>/> >,44
>/> >,40
>/> >,4<
>/> >,4
>/> >,04
>/> >,0
>/> >,=
>/> >,,0
>/> >>?=
>/> >
>/> > ,
>/> > ==
>/> > 4,
>/> > ?3
>/> > >=
>/> > 3
>/> > ,
>/> > <=
>/> > =,
"=
>/>0 4 0
>/>0 4 0
>/>0 4 0
>/>0 4 0
>/>0 4 4
>/>0 4 4
>/>0 4 ?
>/>0 4,
>/>0 4,
>/>0 4,=
>/>?== ,
>/>?=0=
>/>?=4=
>/>?=?0,
>/>?=3=
>/>?0>,
>/>?0 >0
>/>?0 4=
>/>?0 ,?
>/>?0 30
>/>?0,,<
"0
>/>,,40<
>/>,,40<
>/>,,40<
>/>,,40<
>/>,,40<
>/>,,40<
>/>,,40<
>/>,,40<
>/>,,40<
>/>,,40<
>/>,= ,
>/>,= ,3
>/>,= <=
>/>,= =
>/>,= =4
>/>,= 0
>/>,= 00
>/>,= 4
>/>,= 4<
>/>,= 4?
>/>,= ?
%
@A
=
=
=/>>>
=/>>> =
=/>>><4=
=/>>>? ,
=/>> , 3
=/>> >4?
=/>>, 4
=/>><3 0
=/>>4<?3
0/?>>3
0/? >0=3
0/?<><3
0/?0><==
0/??>=??
0/3>>3 ,
0/3 <30
0/3< ,<
0/30,<3,
0/3?>0=4
4
Q
9
@# . A
>/> >,0<
>/> >,0<
>/> >,0<
>/> >,0,
>/> >,0
>/> >,=3
>/> >,=0
>/> >,=
>/> >,<,
>/> >,,
>/> >, =
>/>> <0
>/>> ,=
>/>>
<
>/>>
=
>/>> >0
>/>> 3?
>/>> 3
>/>> ?,
>/>> 44
>/>> 4
>/>> 0?
2!A
> /< 3
> /< 3
> /<
> /<>4
> /,?4
> /,=?
> /, ,
> / <4
> / <4
> >/334
> >/44,
?<?/0? =
?<4/340?
?<4/,
?<0/4
?<0/ <00
?<=/0 =
?<=/ ,<<
?<</0? 3
?<</ 0<4
?<,/3= ?
?<,/0 ?0
9,
>/>>0 33
>/>>0 33
>/>>0,
>/>>0,
>/>>0,
>/>>0,>
>/>>0,>
>/>>0,>,
>/>>0,>=
>/>>0,>4
>/>>0,
>/> <4 =
>/> <443
>/> <? ?
>/> <?4=
>/> <3 ?
>/> <3=?
>/> <33=
>/> =>,
>/> =>0
>/> =>?0
>/> =
2!A
?==/>44
?==/>44
?==/>?<
?==/>3<0
?==/ >,
?==/ ,<
?==/ 03<
?==/
0
?==/,> ,
?==/< 4
?==/0>>=
?=4/3?3
?=4/? 4<
?=4/0=4
?=4/=>4=
?=4/,043
?=4/ ,4?
?=4/ 04
?=4/>><
?=0/?33
?=0/? >3
?=0/4,3,
,
<
=
0
@ 2!A
@ 2!A
@ 2!A
@9A
@ 2!A
4>>?/>?3
></3 , ??,/<3<
<3>
,0>
4>>?/>?3
></3 , ??,/<3<
<3>
,0>
4>>?/>3
></3 0 ??,/<3=3 <3>/>> ,
,0>
4>>?/>3? ></3>== ??,/<3?= <3>/>>,,
,0>
4>>?/ >= ></??34 ??,/=> = <3>/>>0
,0>
4>>?/ 4
></?00 ??,/=>?< <3>/> >0
,0>
4>>?/ ,= ></?,>0 ??,/= 4, <3>/> 4
,0>
4>>?/ 0
></444< ??,/=,>4 <3>/> 4
,0>
4>>?/ >
></034? ??,/==>3 <3>/><
,0>
4>>?/ =3 ></=4?, ??,/=?
<3>/>0<,
,0>
4>>?/,<0 ></,33= ??,/0 4 <3>/>343
,0>
004 /,,
> /> >3 >=,/, 3 =,0/0??=
,0>
0003/<>0 > / ? 0 >=</ >0 =,0/3>4=
,0>
0004/0 < > /,< 3 >==/>
=,4/
,0>
000=/3<4 > /<3 =
>==/4? =,4/,>>,
,0>
000</,34 > /0,
>=0/<?0 =,4/<40
,0>
000 /3=0 > /40
>=4/ < =,4/0,3=
,0>
000 /0 3 > /??,, >=4/4<3 =,4/43
,0>
000>/,4?
> /330 >=?/, , =,4/3, 4
,0>
00=3/ 4 >,/ >>? >=?/?,0 =,?/>0 3
,0>
00=?/,0? >,/ 43
>=3/ 0 =,?/ =3
,0>
00=4/<4= >,/ 0>4 >=3/0, =,?/ 0>
,0>
9
@# . A
#
0/=, .>=
0/=, .>=
0/=, .>=
0/=, .>=
0/=, .>=
0/=, .>=
0/=, .>=
0/= .>=
0/= .>=
0/= .>=
0/= .>=
/?< .>=
/?, .>=
/? .>=
/? .>=
/?> .>=
/43 .>=
/43 .>=
/4? .>=
/44 .>=
/44 .>=
/40 .>=
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
=>
@ 216!A
>/>> 4<
>/>> 4<
>/>> 4<
>/>> 4<
>/>> 4<,
>/>> 4<=
>/>> 4<?
>/>> 4=
>/>> 4=3
>/>> 40?
>/>> 4?,
>/>><03
>/>><,,<
>/>>,334
>/>>,043
>/>>,,43
>/>>,>3?
>/>> ?,<
>/>> =?0
>/>> ,==
>/>> ?
>/>> >>0
,
@ 216!A
.>/>>?3,<
.>/>>?3,<
.>/>>?3,<
.>/>>?3,=
.>/>>?3,=
.>/>>?3,=
.>/>>?3,=
.>/>>?3,0
.>/>>?3,4
.>/>>?3,3
.>/>>?3<
.>/>>,4 4
.>/>>,<,=
.>/>>, 0?
.>/>> 3 0
.>/>> 043
.>/>> <=0
.>/>> <4
.>/>> >=
.>/>> ?0?
.>/>> 4,
.>/>> =3
,
>/<= 33
>/<= 33
>/<= >0
>/<= 4
>/<= ,,
>/<= =4<
>/<= 3,?
>/<=,<?<
>/<=<,>=
>/<===<
>/<=4,34
>/40 ?0
>/4, ?=,
>/4>,3>0
>/04=<=
>/0<4<34
>/0 >>=
>/=3, 0
>/=004><
>/=<>?
>/= ><3?
>/<33 >?
>/4344 ,
>/4344 ,
>/4344,
>/4344<<
>/43440
>/43443
>/434?,
>/434?3=
>/4343?3
>/43? 3
>/43?,,?
>/=?>3>3
>/==?0?
>/=,043?
>/= = 0?
>/<3<>30
>/<4, 3
>/<= ?=?
>/<, ?>=
>/< , <
>/,3403
>/,? <34
=( 7
"
"
>/>33? 4
>/>33? 4
>/>33? 0
>/>33? =
>/>33? ,
>/>33?
>/>33?>0
>/>33?
>/>3343
>/>33444
>/>334=0
>/>?=4?,
>/>?=4 4
>/>?=04=
>/>?=0 4
>/>?==?
>/>?==<
>/>?==>
>/>?=<0=
>/>?=<,
>/>?=<>4
>/>?=,?
",
>/>?,=0
>/>?,=0
>/>?,=0
>/>?,=0
>/>?,=0<
>/>?,=00
>/>?,=4
>/>?,=40
>/>?,=?<
>/>?,=30
>/>?,0 <
>/>?04 <
>/>?04
>/>?04
>/>?04 ?
>/>?04 0
>/>?04 =
>/>?04 ,
>/>?04
>/>?04
>/>?04>3
>/>?04>?
>/0?<?=
>/0?<?=
>/0?<?=
>/0?<?=,
>/0?<?=<
>/0?<?=0
>/0?<?=3
>/0?<?0,
>/0?<?4
>/0?<?43
>/0?<?3<
>/04<, =
>/04< =
>/04< ?
>/04< =
>/04<>==
>/04,33?
>/04,3<0
>/04,?34
>/04,?=
>/04,? ?
>/04,4?=
>/3?00<
>/3?00<
>/3?00,0
>/3?00,
>/3?00
>/3?00>0
>/3?0=?=
>/3?0==,
>/3?0=>=
>/3?0<,,
>/3?0, =
>/30, ??
>/30=3,,
>/30?<=,
>/34>?<?
>/34,
>/34= 4,
>/344,>4
>/343 <
>/3? > 3
>/3? ,3,
>/3?,44
5
@2
9A
,,/4?,>
,,/4?,>
,,/4?,><
,,/4?,>3
,,/4?, =
,,/4?, =
,,/4?,,3
,,/4?,0
,,/4?,3<
,,/4?<<,
,,/4?= 4
,=/>?4<
,=/>3< ,
,=/ >>,4
,=/ >0 ?
,=/
=?
,=/ 00
,=/
4
,=/ ==3
,=/ 30
,=/ , =3
,=/ ,==3
,
>/3=333,
>/3=333,
>/3=333,
>/3=333
>/3=333
>/3=33?4
>/3=33?,
>/3=3344
>/3=330?
>/3=33==
>/3=33,=
>/34? >
>/34343
>/3? ,>
>/3? 4,0
>/3?<>3<
>/3?=,4?
>/3?0=3
>/3?44,
>/3???>,
>/3?30 ,
>/33><,
) 0 $
,,
"<
>/> > =,
>/> > =,
>/> > =,
>/> > =
>/> > =
>/> > <?
>/> > <<
>/> > ,3
>/> > ,
>/> >
>/> > >,
>/> >,
>/> >,,
>/> >,<?
>/> >,0=
>/> >,?
>/> >,3=
>/> ><>3
>/> ><
>/> ><,,
>/> ><<
>/> ><=
"=
>/>?0,,?
>/>?0,,?
>/>?0,,?
>/>?0,,?
>/>?0,,3
>/>?0,,3
>/>?0,<
>/>?0,<
>/>?0,<<
>/>?0,<?
>/>?0,=,
>/ >0<0?
>/ >0=40
>/ >0040
>/ >0403
>/ >0?=0
>/ >03,0
>/ >4>
>/ >4>?
>/ >4 <<
>/ >4 3
>/ >4 <
"0
>/>,= ?
>/>,= ?
>/>,= ?
>/>,= ?
>/>,= ?
>/>,= ?
>/>,= ?
>/>,= ?
>/>,= ?
>/>,= ?
>/>,= ?
>/>,0,??
>/>,0,3=
>/>,0<>
>/>,0<>0
>/>,0<
>/>,0< 0
>/>,0<
>/>,0< =
>/>,0< 3
>/>,0<,
>/>,0<,<
II
II
/ ;/
C
>
: C 34 /
/ /B/
! C
%
,/ 9/ / H
.I$!!
;/B/ B
</ / 5! C @""
=/ / / B 6 C>
0/ / H C
/C, >
5
4/ / /
/ /
C,
/
( 5/
34/
/ >>>(
5 !!/
C?
C 330/
) *( 5/ . >/
/ >>,/
/,
/ 333(
C 3?=/ ( 5/ . 3/
>
,<
/
/ 333(

Transport Phenomena: Giulio Lolli

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Transport Phenomena: Giulio Lolli

Uploaded by

Copyright:

Available Formats

Modern Methods in Heterogeneous Catalysis Research

Fundamentals of M,H&M Transfer

Chemical Engineering Handbook

Why Transport? Catalytic Process

2nd Law (variation in space-time)

2nd Law (variation in space-time)

Math 101- Gradient

Math 101 Nabla, Gradient

Math 102 Divergence, Laplacian

Math 102 Divergence & Laplace

Math 102 Divergence, Laplacian

Math 103 Substantial Derivative

Math 103 Substantial Derivative

Math 103 Substantial Derivative

Fundamental equations of the system

Start-up in circular tube

Example: startup in circular tube only uz (r) != 0

In S.S. conditions (/t = 0)

Finite elements approach

Set up the correct problem and boundary conditions

All the phenomena happen in the boundary layer

outside the boundary layer is in equilibrium

The boundary layer is very thin

size of the boundary layer () is smaller than the

Boundary layer approach

Extension to Macroscopic Balances

Overall Transfer Coefficient

Extension to macroscopic balances

1/U = 1/hint + s/kmetal + 1/hext

Sphere in laminar flow

Log-Mean Temperature Difference

Extension to macroscopic balanc

1/U = 1/hint + s/kmetal + 1/hext

Momentum, Heat and Mass Transfer

order PDE numerical solutions

Produced from SynGas

Typical plant size is 1 Million ton/year

Low operating temperatures minimize the catalyst sintering rate

Close approach to equilibrium is achieved and maintained

Easy to reduce and start-up

KATALCO 51-8 is a copper catalyst on a ZnO-Al2O3 support with a MgO

Chemical Composition (Typical)

KATALCO 51-8 catalyst is available in non-returnable polythene lined

m2 section approx 4 m diameter

-56789:;86<) =>87) ?:@@:=) A56B5;CD=856) =>:) ?;:77E;:) 9;5?) DA;577

Internal Mass Transfer Limitation

No external limitations in terms of gas composition

1st bed 580 490 K

MW power to take out

kg/s steam produced

tube heat exchanger: 2 (5cm) tubes

HEAT AND MASS TRANSFER

For example, vapori

1st bed 580 490 K

MW power to take out

kg/s steam produced

tube heat exchanger: 2 (5cm) tubes

pressure steam 1-2 atm 120C

Fundamentals of M,H&M Transfer

Chemical Engineering Handbook

' 6' ",(

& ' &

" ' " !