Nghiên cứu ảnh hưởng của axit humic đến sự di chuyển của một số kim loại nặng trong các đối tượng môi trường

DAI
HOC
QU6C
GIA HA
NOI
TRUCJNG
DAI
HOC KHOA HOC TLf
NHI£N
D^TAI
NGHIEN
CUfU
ANH
HUONG
CUA
AXIT
HUMIC
DEN SU Dl
CHUYEN
CUA MOT SO KIM
LOAI NANG TRONG
CAC DOI
TUONG
MOI
TRUONG
MA SO
:
QT -
03
- 27
CHU TRI

Dfi
TAI:
PGS.TS
.
Bui
Du
v
Cam
CAC CAN
Bp
THAM GIA:
-TS.
Pham
Van
Tinh
-ThS.
Nguyen
Bao
Cham
DAI
HOC
QUOC
GIA HA
NO*
TRUNG
TAM
THONG
TIN
THU
VIL'

N
or/
^36
HA NOI 2005
MUC LUC
Trang
Bao cao torn
tat
Mddau
Chuong 1
Axit
humic va vai tro
ciia
no trong moi trudng
1.1
Su ton tai
ciia
axit humic trong
lir
nhien
1.2
Thanh phan va cau tao
ciia
axit humic
1.3
Tfnh chat
ciia
axit humic
1.4
Vai trd cua axit humic trong

xii
ly
moi
trudng
Thuc nghiem
Dung cu, thiet hi
Vat lieu
Hoa chat va thudc thu
Phuong phap nghien cuu
Piui'tm^
phdp
ns^lucn cihi tinli
PhU(/ni^
phdp
nghien cUu
dong
Phuang phap phan
tich
kim loai
Phiurng plidp
xdc dinh Ph
(H)
Phif(/nsi
phdp xdc dinli Cd
(H)
PliU(/Hi^
pluip xdc
diidi
Cu
(//)

PhU(my,
phdp xdc dinh Zn (H)
PhU(my,
phdp phdn tich As
Ket qua va thao luan
Nghien cuu kha nang hap
giu
cua axil humic ddi
\'di
Ph '
Ni^hicn
cuu anh
hUony,
cua pH
den
kha
ndnsj,
hdp
•^iil
Ph
'
Nghien cihi
dnh hudng cua thdi
i^ian
den kha
ndn_'^
hap
.i,'//?'
Nghien
ciiu

kha nang hap giu cua axil humic \'di
Cu^*
Chuong 2
2.1
2.2
2.3
2.4
2.4.1
2.4.2
2.5
2.5.1
2.5.2
2.5.3
2.5.4
2.5.5
Chuong 3
3.1
3.1.1
3
1.2
3.2
2.1
Nghien
ciiu
anh hudng cua pH den kha
ndn<.^
hdp
.L;//7
2.2 Nghien
diu

d/ih
hU(hii> chia
thdi gian den kha ndng hdp gill
3.3 Kel qua nghien cuu kha nang hap
giu'
cua axit
huinic vdi
Zn''
3.1
Nghien (
uu anh
hii'chig
cua pH
den
kha ndng hap
gift
3.2 Nghien
cUu
anh huong cua thdi gian den kha
nd/i'^
hap
;^iu
3.4 Nghien cuu kha nang hap giu cua axil humic
\
di
Cch'
4.1
Nghien cuu anh
hiuhig c
ua pH den kha ndng hdp

giil'
4.2 Nghien
eu'u
anh
hiuhig
cua thdi
gian den
kha ndng hap
giil'
^.5
Ket qua nghien cuu kha nang hap giucua axil huinic \'di Asen
5.1
Kel qua nghien cuu kha ndng hdp
giU
As
(11/)
cua axil humic
5.2
5.^
5.4
3.6
3.7
Ket qua nghien
cii'ii
kha ndng hap
gitl'
As (\'}
hoi axil hiiinu
Kel qua nghien cuu kha ndng hap
^^iu

As
M / hoi
a\ii
huniu
khi
CO nidi
cua
Fe''
Nghien
eu'u
kha ndng hdp
giil'
A.\
cua sal
liunial
Nghien cuu anh hudng cua mot so dien
1\
den qua
trinii
hap
giu"
Cch*
Tiich cac ion kim loai tren cot chua axil
hunuc
6
Ket
luan
7
Tai
lieu tham khao

1
6
7
7
7
9
11
14
14
14
15
15
15
16
17
17
17
18
18
20
2f)
20
23
25
25
28
30
30
33
36

36
3X
41
41
42
42
43
45
46
49
50
BAO
CAO
TOM
TAT
Bt
TAI
•
l.Ten
de
tai;
Nghien
cAu
dnh huang cua axit humic den su di chuyen ctia
mot so kim loa nang trong cdc doi
tuang
moi
tru&ng
2.Maso;
QT-03.27

3.Chu
tri
de
tai:
Biii Duy Cam
4.Cac can bo tham gia:
-TS. Pham Vdn Tinh
-ThS. Nguyen Bdo Cham
5. Muc tieu va noi dung nghien
cihi
:
- Nghien
cihi
kha nang phan
ling
cua axit humic vdi cac kim loai nang
trong moi truang nu6c.
- Nghien
ciJu
cac yeu to anh hudng den kha nang hap
phii
cac ion kim
loai nang ciia axit humic.
- Nghien
cihi
kha nang
sir
dung axit humic lam chat hap
phii
tach cac

ion kim loai nang ra khoi dung dich nudc.
6. Cac ket qua dat duac
6.1
.Ket
qua khoa hoc
- Ve khd ndng phdn dng cua axit humic vai cdc kim loai nang trong
moi trudng nuac:
La mot axit
hiJu
ca chua trong phan
tir nhi^u
nhom chiic hoat dong nhu
cacboxyl,
phenolic hydroxyl, nito di vong, amino tham nen axit humic
la
mot
hgp
chat rat hoat dong ve mat hoa hoc. No co kha nang tham gia phan
ling trao doi cation, tao ket tiia, tao phiic vdi nhieu hap chat vo ca va
hiJu
ca.
Axit humic cd the tao phiic tan hoac khdng tan vdi
nhi6u
ion kim loai nang
va phdng xa.Vi vay, trong cac nguon nudc axit humic dugc xem la tac nhan
ldi keo va phan tan cac kim loai nang d trong cac nguon nudc. Kha nang
1
phan ling cua axit humic vdi cac ion kim loai nang
Pb^"",
Cu""^,

Zn^"",
Cd^"",
As^"", As^^
da dugc nghien
ciiu.
Ket qua cho thay axit humic
r^n
cd the hap
phu kha manh cac ion kim loai nay
- Ve cdc yeu to dnh huang den khd ndng
hdp
phu cua axit humic.
Mot so yeu to' da dugc nghien ctiu la pH dung dich, thdi gian phan
ling,
sir
cd mat
ciia
chat dien ly. Trong
viing
pH tii
1
den
6,
neu pH cang tang
thi
hieu
suat hap phu cang tang.Tuy nhien viing pH thfch hgp nhat la 4,5 den 5,5 va
khoang 70% den 98% lugng kim loai trong dung dich cd the dugc hap phu. 0
viing pH cao hon
dt

xuat hien
sir
thuy phan ciia cac ion kim loai nay. Thdi
gian phan ling dugc nghien
ciiu tir
20 den 360 phiit. Sau 20 phiit hieu suat
hap phu da dat tii 50% den 70% doi vdi ca hai loai axit. Cac chat dien ly hau
nhu khdng anh hudng den phan
ling
cua axit.
-
Ve
khd ndng su
diojg
axit humic de tdch kim loai nang khoi dung
dich nUdc.
Kha nang
sir
dung cot trao doi chiia humic dang
r^n
da dugc nghien
ciiu.
Ket qua cho thay cd the
sii
dung cot chiia axit humic dang
rdn
dugc tach tii
than biin ciia Viet Nam de tach cac ion
Pb^"^,
Cu^"^,

Zn^"",
Cd^'^khdi
nudc thai
cd mdi trudng axit. Hieu suat tach d pH
=
4,6 - 4,8 dat 98%.
B^ng
phuang
phap nay cd the lam giam ndng do cua cac ion nay tii 20mg/l xudng cdn
0,004mgA-
- Ve cong trinh dd cong bd: Da cong bd
01
bai bao trong tap chf Phan
tfch Ly Hoa sinh.
6.2. Ket qua dao tao
- 01
Thgc sT
Moi truang
- 01
Cunhdn
Hod
hpc
7.
Tinh hinh su dung kinh phi cua de tai:
- Kinh
phi
dugc cap : 20.000.000 d
Kinh
phi
da

sir
dung
Van phdng pham
Thue khoan chuyen mdn
Vat tu hoa
chat
Quan ly hanh chinh
Hdi nghi, hgi thao, cdng tac
phi
1.000.000
d
7.000.000 d
10.000.000 d
800.000 d
2.200.000 d
XAC NHAN CUA BAN CHU
NHlfiM
KHOA HOA HOC
CHU TRI
D£
TAI
P/H
T^
~IM^^%'
jM^u.'
PUf
PGS.TS. Bui Duy Cam
XAC NHAN CUA
TRUCTNG
DAI HOC KHOA HOC TU NHIEN

KT.HIEU TRUONG
PHO HIEU TRUONG
GS.TS. Trdn Nghi
BRIEF OF PROJECT
1.
Title of project:
The effect of humic acid on mobilization of heavy metals in the
invironment,
2.
Code number : QT- 03 .27
3.
Coordinator :
Assoc.Prof.
Dr. Bui Duy Cam
4.
Participants :
Dr. Pham van Tinh
MS. Nguyen Bao Cham
5. Purpose and contents of
project:
- To research the reaction of humic acid with some heavy metals in
solution.
- To determine the factors influenced on adsorption capacity of
heavy metal ions by humic acid.
- To use solid humic acid for decontaminating polluted water by
heavy metals.
6. Activities and main results :
- Humic acid - the fraction of humic substances that is not soluble in
water under acidic condition (pH < 2 ) but is soluble at higher pH
value.

- Humic acids are used most effectively in particular in the stage
subsequent to chemical treatment of water. Due to their outstanding
properties of adsorption of liphophlic substances, their high cation exchange
capacity, their ability to form hardly soluble complexes with polyvalence
cations and heavy metals and their high electron exchange capacity, hmic
acids are ideal as sorption medium for a number of water impurities and
especially for heavy metals and liphophlic substances.
In our works, we prepaired two kindes of humic acid. One is from peat of
Vietnam, one is comercial product of Wako company in Japan and compared
their adsorption properties , The complexation of humic acid with cations
Pb^"^,
Cu^"^,
Zn^"^,
Cd^"^,
As^"", As^
was
studied.The
adsorption capacity of
humic acid depends on pH value of solution and increases with increase of
pH (range from 1 to 6 ). After 20 minutes, about 70% to 98% these ions
absorbed on solid humic acid at pH
=
4.5 - 5.0 .
We have shown that humic acid packed column 9(0.15 - 0.45 mm
particle diameter) can remove 98% these ions at pH
=
4.6- 4.8. The
extraction effiences were highest for
Pb^"^,
Cu^"^and

lower for
Zn^"^,
Cd^"^.
Arsenic was not absorbed by humic acid.
MO
DAU
Cung vdi su gia tang dan sd va phat trien khoa hgc cdng nghe ma nhu cau nudc
sinh hoat cua cac qudc gia ngay cang tang manh. Song, hien tai van de d nhilm cac
ngudn nudc (nudc
ng^m,
nudc be mat, nudc sinh hoat, nudc thai) cang cd xu hudng
gia lang d
nhi6u
nudc, trong dd cd Viet Nam.
Tha'y
dugc tam quan trgng cua viec khai thac, bao ve va
sii
dung hgp ly ngudn
nudc ma nha nudc ta da dua ra nhieu
chinh
sach vt van dt nay.
nhi6u
hgi thao qudc
gia va qudc te to chiic tai Viet Nam da de cap den viec phan tfch danh gia chat lugng
cac ngudn nudc, dua ra cac cdng nghe
xir
ly nudc d nhilm
Trong sd cac chat gay d nhilm, kim loai nang (trong dd cd As) la ddi tugng
dugc quan tam dac biet. Theo cac sd lieu da cdng bd thi d mot sd nai cua Viet Nam ,
ham lugng kim loai nang trong cac ngudn nudc da vugt qua gidi han cho phep. Chinh

vi vay, viec
xii
ly tach kim loai nang ra khdi cac ngudn nudc la mot nhu cau can thiet
va cap bach.
De tach kim loai nang tii dung dich cd the
sir
dung nhieu phuang phap khac
nhau. Song , phuang phap diing chat hap phu thudng dugc
sii
dung nhieu han ca.
Axit humic cd chiia nhieu nhdm chiic khac nhau nhu: cacboxyl, phenolic
hydroxyl, cacbonyl, nita di vdng, aliphatic va amino tham . Do tfnh chat hap phu, kha
nang trao doi cation, kha nang tao phiic khd tan vdi cation da hoa tri va cation ciia kim
loai nang, cung nhu kha nang trao ddi electron cao ma axit humic dugc xem nhu la
chat hap phu ly tudng cac tap chat vd ca va
hiru
ca trong nudc. Ben canh dd, axit
humic cdn dugc xem la tac nhan lam dich chuyen kim loai nang d cac ngudn nudc.
Trong dl tai nay, chiing tdi nghien
ciiu
phan
ling ciia
axit humic vdi cac kim
loai Pb, Cu, Zn, Cd, As va kha nang
sii
dung nd de tach kim loai nang ra khdi cac
nguon nudc khac nhau.
Chuong
I
AXIT HUMIC VA VAI TRO CUA NO TRONG MOI

TRUCtNG
l.l.Sir
ton tai cua axit humic trong tu nhien
Axit humic la mot axit
hiiu
ca yeu.Nd la hgp chat cd phan tu lugng
Idn,
cd
chiia nhilu nhdm tham.Nd la chat kem tan, thudng tdn tai dudi dang
rdn
d trong nudc
va
da't.Trong
tu nhien, axit humic tdn tai nhilu d trong cac loai than va bun. Song, chi
cd than
mim
la chiia axit humic vdi ham lugng
ldn(tir
30-90% tuy thugc vao md than
).
Than biin, biin, cac chat humat cung chiia mot lugng dang ke axit humic (tii 5-60%
tuy thudc vao do tuoi cua than).
O Viet Nam, cd the tim thay than biin d hau het cac tinh tii
B^c
vao Nam nhu
Quang Ninh, VTnh Phiic, Ha Tay, Ha Nam,
Bdc
Ninh,
Bac
Giang, Thanh Hoa, Nghe

An, Hue va dac biet cd rat nhilu d viing ddng bang sdng Cuu Long. Tdng trii lugng
than bun
ciia
Viet Nam la khoang 1.033.355.000
m\
O trong nudc ngam, cac chat humic thudng tdn tai vdi ndng do
tir 10 ppb
den
100
ppm.
1.2.Thanh phan va cau tao cua axit humic
Axit humic dugc
hinh
thanh tii qua trinh phan huy ddng thuc vat. Tuy thuoc vao
dilu kien chuyen hoa va ban chat cua ddng thuc vat ma qua trinh chuyen hoa se tao
nen cac axit humic cd ca'u tnic, trgng lugng phan tu va thanh phan hoa hgc khac
nhau.
Axit humic cd khdi lugng phan tu tii 2.000-600.000 dan vi
caebon.
Tuy thugc vao
nguon gdc ma axit humic cd thanh phan khac nhau. Tuy nhien, thanh phan chfnh
ciia
axit humic la cac nguyen td C, H,
O,
N va mdt lugng nhd cac nguyen td khac nhu S, P,
Al,
Fe. Ham lugng cac nguyen td chu yeu nay thudng chiem ty le nhu sau:
Ham lugng C
:
tii

55%-65%
Ham
lugng
H:
til
3%-10%
Ham lugng O : tii 25%-35%
Ham
lugng
N:tir6%-7%
Ham lugng cac nguyen td khac : tu 6%-7%
Cung
cSn
phan biet vdi axit fuvic. Day la axit cd khdi lugng phan
tir tir
500-
2.000 don vi
caebon
va cd cau tnic phan
tir
gan tuang tu axit humic.
Axit humic cd ca'u tao khdng xac dinh. Theo cac ke't qua nghien
ciiu
gan day thi
axit humic la mdt hgp chat tham cd
c^u
tnic polyme vdi nhilu lien ket giiia cac nhdm
tham. Cac hgp chat khac nhau lien ke't trong axit humic la amino axit, amino dudng,
peptit axit
ali

phatic.Axit humic cd chiia cac nhdm chiic khac nhau nhu -COOH,
phenol, ali phatic, enolic hydroxyl, C=0. Axit humic la mdt td hgp cac phan
tir
hinh
thanh nhilu sgi dai d pH tha'p va cau tnic linh ddng cd nhilu
Id
hdng d pH cao. Chfnh
cac
Id
hdng nay cd the
giii
va hap phu cac cha't vd ca va huu ca mang dien tfch trai
dau.
Phan
tir
axit humic cd dang polyme, trong dd cd chiia nhiing hgp chat nhan
tham kieu phenol va cac hgp cha't chiia nita dang vdng va di vdng (indol; purin;
primidin) va cac axit amin. Cac hgp chat tham tao ra nhan tham ciia axit Humic. Cac
cSu
ndi nay cd the la
nhOng
phan
tir
rieng biet (-0-) hoac la nhdm (
-NH2-;
-CH2-)
cung cd the lien ket
true
tiep qua nguyen tu
Caebon

(-C-) [1,2]
Trong cau tao
ciia
axit humic cd :
- Nhdn tham. khi oxy hoa axit humic bdi HNO3, kilm hoac
KMn04
ngudi ta
thay xuat hien nhiing nhan tham. Dd la nhung dan xuat cua phenol, quinon va axit
benzoic. Theo W. Conell cau tnic mdt sd nhdm nhu sau:
OH
OH
OH
OH
OCH CH
3O
OCH
OCH
OCH
OH
COOH
COOH
HO
COOH
Nita trong axit humic
8
Khi thuy phan axit humic bdi mdt axit vd ca
thi
cd
chirng
mdt nua nguyen

tir
nita chuyen vao dung dich. Dd la nhirng amit, mono hoac diamino axit. Mot sd tac gia
cdn
tim
thay ca nhung axit amin cd nhan tham purin, primidin, indol
HO,
H"
H
I
C^^N
HC
HC
^
CH
CH-
CH
^
•CH
CH
HN
HC
N
HC^
C^
^N
^CH
Primidin Indol Purin
- Nhom dinh
chitc
cua axit humic

Trong axit humic cd nhiing nhdm chiic dien hinh la: cacboxyl ( -COOH ), rugu
( -OH ), metocxyl (
-OCH3),
cacbonyl(-C=0), phenol ( -OH ). O mach ben cd chiia
ca nhdm cd ndi ddi (
-C=CH-).
Nhd cac phuang phap hien dai, cac nha khoa hgc
xac dinh dugc axit humic cd 3 - 4 nhdm cacboxyl va tir 3 - 6 nhdm -OH
ciia
rugu va
phenol.
Sa do cau tnic phan tu axit humic cua Dragunov va cdng tac vien nhu sau:
CeHnOs
HO
- Cdc nhom
chitc
ldm cho axit humic co khd ndng tao phiic la: cacboxyl,
phenolic hydroxyl, nita di vdng, ali phatic va cac amino tham. Axit humic cd the tao
phiic vdi ion kim
Igai
giira hai nhdm COO" va OH', giira hai nhdm
COO
hoac mot
nhdm COO'.
1.3. Tinh chat cua axit humic
Axit humic khdng tan trong nudc cd mdi trudng pH < 2 nhung tan dugc trong
kilm va mdt sd dung mdi hiru ca (dimetyl fomamit, dimetyl
sunfoxit).
Axit humic dugc tach ra tuf than bun la chat ket tinh mau den, sang dng anh, khd
bi nhiet phan ngay ca khi nung ndng d

200°C
Nhu da neu trong
phSn
tren, vi trong phan
tir
cd chiia nhdm cacboxyl va phenol
nen axit humic dugc xep vao loai axit huu ca yeu. Cac nhdm chiia axit trong phan tir
humic cd cudng do axit khac nhau, ke ca cung loai caboxyl hoac phenol nhung neu d
vi tri khac nhau se cd cudng do khac nhau. Gia tri pKa
ciia
nhdm caboxyl nam trong
khoang tir 4 - 6, cdn pKa cua nhdm phenol cd gia tri tir 9 -
11.
Su cd mat ciia cac nhan tham vdi cac electron p linh ddng va cac nhdm chiic
khac nhau lam cho axit humic cd kha nang
thiic
hien phan ling trao ddi ion, tao phiic
va oxyhoa- khu. Khi trao ddi cation, cac vi tri tren phan tir humic gan nhu dugc lap
d^y
cation hydro.
Cac cha't humic gan nhu hoan toan tfch dien am do cd chiia mot lugng
Idn
cac
nhdm chiic cacboxylic, phenolic. Do qua trinh hydrat hoa cac nhdm tich dien va luc
day
tinh
dien ma cac chat humic hoa tan d trong nudc dugc phan bd rgng han do su
thay ddi dilu kien mdi trudng. Axit humic dugc xem la cau tir quan trgng trong dat va
nudc'
Dua vao ke't qua thuc nghiem nghien

ciiu
tuang tac cua axit humic vdi cac cation
kim loai nhu
Cu^"^,
AP"",
Zn^"^,
Mn^"^,
Fe^""
cac tac gia da ket luan axit humic la chat
cd kha nang tao phiic manh vdi ion kim loai.Trong phan
ling,
cac cation kim loai da
the nguyen tir hydro cua cac nhdm chiic trong phan tir axit humic de hinh thanh nen
phiic chat
[2,4].
Phan ling giira axit humic vdi cation kim loai cd the tao nen hgp chat vdi cac
kieu lien ke't khac nhau.
- Lien ket ion: tao nen cac mudi di
cue
humat cua cac cation kim loai hoa tri
1,
2 theo kieu:
(COOMe)„
^ ^
(OMe)^
Trong dd Me la kim loai hoa tri 1,2
10
- Lien ket phdi tri: Tao thanh cac mudi phiic Cd the cd 2 loai phiic: Phiic
thudng (neu trong phiic cd 2 loai lien ket ion va lien ket cdng hoa tri) phiic ngi (neu
trong phiic cd 2 loai lien ket ion va kieu lien ket phdi tri, trong dd phan tir hiiu ca la

phdi ttr cdn Me la cha't tao phiic).
- Lien
ket
phdn
tU:
Tao nen khi axit humic tuang tac vdi cac oxyt
R2O3
hoac
khoang set. Vai trd
ciia
axit humic trong kieu lien ke't nay gidng nhu chat ket dfnh,
lien ket cac hat khoang trong da't lai vdi nhau.
Khi diing axit humic de ket tua dinh lugng kim
loai
thi tuang tac
ciia
axit humic
vdi kim loai la tuang tac hoa hgc
chii
khdng phai la hap phu vat ly thdng thudng. pH
cua mdi trudng cd anh hudng manh de'n do
bin
cua phiic.
Pandey A.K va cac cdng su [23] cho thay: axit humic vdi nhdm chiic hydroxyl,
phenoxyl, cacbonyl cd the tao thanh hgp chat phdi trf vdi kim loai. Nghien
ciiu
su tao
phiic d
pH=
3,5

cho tha'y hang sd
bin (logk)
cua phiic dugc tao hinh thanh giua axit
humic va cac kim loai khac nhau giam theo trat tu sau: Cu > Fe > Pb > Ni > Co > Ca >
Cd > Zn > Mn > Mg. Ngoai pH mdi trudng, kha nang trao ddi cation, ban kfnh phan
tir va dien tfch bl mat phan tir
ciia
axit humic cung anh hudng den do
bin ciia
phirc
Viec xac dinh hang sd
bin ciia
phiic giiia axit humic vdi cac nguyen td: Be, Ca,
Sc,
V, Cr, Mn, Fe, Co, Zn, Ga, Sr, Y, Ba, Ce, Eu, Gd, Tm, Yb, Lu, cho thay nhung ion
cd dien tfch
Idn,
ban kfnh ion nhd se tao phiic
bin
han. Vj trf tao phiic
la
nhdm
cacboxylat [ 3 ] .
1.4. Vai tro cua axit humic trong xu ly moi trudng
Cac nha khoa hgc mdi trudng tir lau da rat quan tam den cac cha't humic vi phan
ling
ciia
nd vdi dat va nhung chat d nhilm trong nudc cung nhu anh hudng
ciia
nd de'n

qua trinh xir ly. Song, nhiing cdng bd vl
ling
dung thuc te
ciia
cac chat humic trong
cdng nghe mdi trudng cdn chua
nhilu.Hau
het cac nha khoa hgc da sir dung cac chat
humat de tach kim loai khdi nudc hoac tach kim loai nang trong
dat.Phan ling
giua cac
chat humic vdi chat thai hoa hgc dgc hai se xay ra khi hoa chat nay dugc thai xudng
dat.Yeu
td
chii
yeu dugc quan tam trong phan ung
ciia
axit humic vdi chat thai hoa
chat la do tan
ciia
cac vat lieu humic. Cac chat humic dich chuyen trong mdi trudng
vdi mdt lugng
Idn
la do tiep
xiic
vdi chat thai kiem vf du nudc thai tach luu huynh tir
11
san
ph^m
dau md. Cac cha't humic trong dung dich cd the dugc ke't

tiia
khi tie'p
xiic
vdi
nudc thai cd mdi trudng axit hoac chiia ion kim loai da hoa
tri.
Kha nang phan
ling
tao phiic chelat vdi ion kim loai
ciia
axit humic da dugc
nhieu tac gia nghien
ciiu.
Phan
ling
nay phu thugc vao cac yeu td sau: Ban chat cac
cha't humic; ban cha't
ciia da't
va mdi trudng nudc nhu do axit, kilm; kha nang oxyhoa-
khir; su cd mat
ciia
cac cha't canh tranh
(vi
du xyanua canh tranh vdi humic ddi vdi ion
kim loai).Trong mot sd trudng hgp, axit humic cdn ngan can phan
ling
tao ke't tua cua
kim loai vdi mot sd anion nhu cacbonat, hydroxyt, sunfua.Axit humic cd the lam tang
do tan
ciia

thuy ngan len 1000 lan. Nhu vay, neu dung axit humic de tach kim loai ra
khdi nudc bang phuang phap ke't
tiia
trong trudng hgp nay se khdng cd hieu qua.
Mot anh hudng khac cua axit humic ddi vdi kim loai la phan
ling
oxyhoa-khir.
Phan ling nay xay ra theo 2
each:
Axit humic ddng vai trd la mot tac nhan khir vdi the khir la
E^=
0,7 V gdn
bang the khir cua Fe(III).
Axit humic lam
bin
viing cac cation kim loai cd tfnh khir trong dung dich
bang phan ling tao phiic chelat va do vay lam tang kha nang khir
ciia
cac
oxoanion ( nhu
Cr07^'
,Mo04
^').
Su dich chuyen, phan
ling ciia
cac hgp chat hiru ca khdng phan
cue
trong mdi
trudng nudc chiu anh hudng cua cac chat humic tan, keo hoac khdng tan trong dd. Do
kha nang phan ling dugc vdi nhilu kim loai va cac chat hiru ca nen axit humic la mot

trong nhiing tac nhan van chuyen kim loai nang d trong cac ngudn nudc ngam va nudc
be mat. Axit humic vi the da dugc nghien
ciiu
sir dung trong cdng nghe xir ly mdi
trudng de tach loai cac cha't ddc vd ca va hiiu ca. Trong cdng nghe mdi trudng, axit
humic dugc
ling
dung theo mdt so hudng chu ye'u sau day:
- Trung hoa nudc thai axit
- Tach kim loai nang bang tao phiic chelat hoac ket
tiia
humat khdng tan.
- Tach cac anion nhu photphat, xyanua va cac anion hiru ca bang tao phirc vdi
phdi tir hdn hgp.
12
- Ha'p phu cac cha't ddc hiiu ca de lam tang kha nang xir ly ngudn nudc thai
bang phuang phap sinh hgc
- Tach cac cha't la lirng bang ke't tua hoac lam ndi len.
Vermeer va cong su da nghien
ciiu
kha nang hap phu Cd len hdn hgp axit humic
va hematit. Ket qua cho tha'y, hieu qua tach Cd td't hon so vdi viec dung rieng re cac
cha't humic hoac hematit. Gia tri pH cua mdi trudng cd anh hudng de'n su hap phu.
Do phan
ling
giua axit humic mang dien am va oxyt sat mang dien duang ma su hap
phu ion kim loai len axit humic (trong hdn hgp) se giam di so vdi axit humic tinh
khiet. Vi the tdng ha'p phu dd'i vdi kim loai len hdn hgp se nhd han so vdi du doan
theo quy tac cdng tfnh. Trong trudng hgp nay, ion kim loai cd ai
lire

vdi axit humic ro
ret hon so vdi oxyt khoang. Ngugc lai, tdng ha'p phu kim loai se
Idn
han trong trudng
hgp ion kim loai cd ai luc ddi vdi oxyt khoang manh han so vdi axit humic.
Axit humic thd vdi kfch thudc hat 0,1 - 0,6mm cd the dugc diing nhu la mdt tac
nhan chiet dang ran de xir ly nudc thai cd chiia
Pb^^
Zn^^
Ni^^
Ca^^
Sn^^
Cd^%
As^\
Mg^""
trong mdi trudng axit. Hang sd
bin
dilu kien
(logK) ciia
phirc kim loai - humic
(trong than
mim)
cd gia tri tir 4,6
-
5,5. Hap dung tfch theo mg kim
loai/g
axit humic
cua cdt la 0,15 (ddi vdi
Ag"*^)
va 2,22 (dd'i vdi

Pb^"^).
Hieu qua tach
ciia
cdt chira axit
humic la cao nhat dd'i vdi
Pb^"",
Cu^"^,
Sn^"",
va thap nhat ddi vdi
Mg^"^.
Axit humic va
nhiing
san pham the
ciia
nd da dugc sir dung de tach loai kim loai
ddc khdi nudc thai. Axit humic la chat cd hieu qua de xir ly nudc bang phuang phap
hoa hgc sau khi thuc hien phuang phap ke't
tiia
hydroxyt. Viec them axit humic se
lam tang qua trinh ke't tua kim loai. Bang phuang phap nay cd the lam giam ndng do
kim loai trong nudc thai thap han 0,03mg/l. Hieu qua nha't
ciia
phuang phap nay la
ddi vdi
Pb'^
Hg'\
Cd'\
Cu-^
Zxi^\
Ni'^

Cr^^
Do tfnh chat hap phu, kha nang trao ddi cation, kha nang tao phiic khd tan vdi
cation da hoa tri va cation kim loai nang, kha nang trao ddi
ciia
electron cao ma axit
humic la chat hap phu ly tudng cac tap chat trong nudc De xir ly nudc ngam, cd the
bam axit humic long vao kenh nudc ngam.
Axit humic cd do tan giam d pH thap va cd do tan rat thap d pH
=
2. Do vay,
axit humic rat cd gia tri de lam sach nudc thai cd mdi trudng axit. Axit humic ddng
mot vai trd quan trgng trong chu trinh dia hoa cung nhu dac tinh
ciia
nhilu cau tir hoa
13
hgc trong mdi trudng bien. Axit humic cd the tao phiic vdi cation kim loai va dilu nay
dan
den su di chuyen va phan bd lai cac kim loai giiia nudc va tram tich.
Tir axit humic ngudi ta cd the che tao chat hap phu HUMASORB. Chat nay rat
cd hieu qua de tach cac kim loai nang, kim loai kiem va phdng xa, cac hgp chat huu
ca. Khi dung 0,2gam
chaft
HUMASORB vdi thdi gian phan
ling
trong 2 gid d
25°C
da
ha'p phu dugc 98% Ce, Pb trong 25ml cd ndng do Ce, Pb ban dau la 200 ppm. Ca che
tach d day gom ca 2 loai: trao ddi ion va tao phiic vdng cang .
CHLfONG 2 - THlTC NGHlfiM

2.1.
DUNG
CU
- Cdc thiiy tinh, pipet, buret
,binh
dinh
miic
,binh tam giac cac
loai
- May do pH vdi dien
cue
thuy tinh td hgp: Denver - BASIC
- May do quang:
Jen
way 6400 spectrophotometer
- May ha'p thu nguyen tir: GA900
-
can
phan tich (do chfnh xac ± 0,2mg)
2.2.
VAT LIEU
De tie'n hanh nghien
ciiu,
chiing tdi da dung hai loai axit humic: mot loai la axil
humic thuang mai
ciia
hang Wako - Nhat Ban (dugc ky hieu la axit
HAI)
va mdt loai
dugc tach tir than

biin
cua Viet Nam (dugc ky hieu la axit HA2).
Tdch vd tinh che axit humic tit
than
bun Viet Nam
- Than
biin
dugc xir ly ban dau vdi axft, hoa tan trong kilm rdi dugc ke't
tiia
lai
bang axft. Lgc, rira - lap lai cac qua trinh hoa tan trong kiem, ket
tiia
lai vdi axft. Lgc,
rira tdi pH
^
2 vai lan. Hong khd, cudi ciing say d nhiet do nhd han
80"C
- Xac dinh ham lugng axft humic theo phuang phap [7] .
14
Giii cac san pham axft humic trong
Ig
kfn. Trudc khi dung,dugc nghiln nhd tdi
kfch thudc
cdn
thiet.
•
2.3, HOA CHAT VA THUOC
THU^
Cac hda cha't dugc diing
diu

la loai tinh khiet phan tfch: PA hoac AR
Pb(N03)2.H20,
Zn(N03)2.H20,
CdCl2.2,5H20
,
Cu(N03)2.H20,
AS2O3
CH3COOH, HNO3, HCl, NaOH, dung dich dem axetat
pH4,3;
5 , chi thi xylen da cam,
dung dich nudc brom, hydrazyl sunfat -
N2H4.HSO4
amoni molipdat -
(NHAM0A4.4H2O
2.4.
PHirONG
PHAP
NGHlfiN
ClTU
Trong dl tai nay chiing tdi thuc hien nghien
ciiu
dgc lap timg kim loai vdi cac
yeu td nhu: pH, thdi gian, cac cha't dien ly anh hudng den kha nang hap giir cua axft
humic. Sau khi thuc hien cac nghien
ciiu tinh
de tim ra dilu kien tdi uu
ciia
phan
ling
chiing tdi nghien

ciiu
vdi hdn hgp cac kim loai va cho chay qua cdt cd chiia axft humic
d dang hat nhd de xem xet kha nang tach chiing ra khdi ngudn nudc. Phuang phap nay
dugc ggi la phuang phap nghien
ciiu
ddng.
2.4.1.
Phuang phap nghien
cihi tinh
-
can
0,100g axft humic cua hang Wako da dugc tinh che lai va
ciia
Viet Nam,
nghiln nhd vdi kfch thudc < 0,45mm, cho vao binh tam giac 250ml.
- Lay vao cdc loai 100ml: 40ml dung dich kim loai can nghien
ciiu
cd ndng do
Img/ml,
sau dd diing
CH3C00Na,
HCl, NaOH dilu chinh pH den cac muc khac nhau
(kiem tra bang may do pH), rdi dinh
miic
50ml va dd vao binh tam giac da cd 0,100g
axft humic vira neu tren, lac
diu
trong hai tie'ng ddng hd. Tien hanh lgc qua giay lgc
bang xanh
(I^l

1.
Thu lay dung dich lgc
- Tien hanh phan tfch de tim ndng do kim loai cdn lai trong dung dich lgc va
xac dinh chfnh xac lugng kim loai nghien cim bi hap giir bdi axft humic.
15
Cac budc thf nghiem nghien
ciiu
anh hudng
ciia
thdi gian phan ung dugc tien
hanh nhu sau:
-
can
0,100g axft humic
ciia
hang Wako da dugc tinh che lai va cua Viet Nam,
nghien nhd vdi kfch thudc < 0,45mm, cho vao binh tam giac 250ml.
- La'y vao cdc loai 100ml: 50ml dung dich kim loai can nghien
ciiu
cd ndng do
1
mg/ml, sau dd diing
CHgCOONa,
HCl, NaOH dilu chinh pH den gia tri ma tai dd
kha nang ha'p giii cua axft humic td't, sau dd dd vao binh tam giac da cd 0,100g axft
humic viia neu tren va lac
diu
trong nhiing khoang thdi gian khac nhau tir 10 phiit de'n
6 gid. Tien hanh lgc qua giay lgc bang xanh
OH

ngay sau khoang thdi gian da dinh.
- Tien hanh phan tfch ddi tugng nghien cuu cdn lai trong dung dich va xac dinh
chfnh xac lugng cac kim loai bi hap giu bdi axit humic
Khao sat anh hudng
ciia
mdt sd chat dien ly thudng cd trong mdi trudng nha't la
trong nudc thai cua dung dich ma den phan
ling
dugc tien hanh nhu sau;
- Cho them vao dung dich nghien ciru nhirng chat dien ly nhu:
(NH4)2S04,
K2SO4,
NaCI
,KC1.
- Tien hanh phan tfch ndng do kim loai nghien
ciiu
cdn lai trong dung dich de
tim ra lugng kim loai bi ha'p giii bdi axft humic.
2.4.2.
Phuong
phap nghien
cihi
dong
Pha hdn hgp dung dich cac kim loai nghien ciru vdi ham lugng nhat dinh rdi
dieu chinh pH thfch hgp, sau dd cho chay qua cot nhdi 4g axft humic (hat cd kfch
thudc trong khoang tir 0,15mm de'n 0,45mm, dudng kfnh cdt 12mm, tdc do chay ban
dau dieu chinh 3ml den
4ml/phiit,
nhiet do phdng khoang
32''C.

Mdi 1ft dung dich hdn
hgp dugc khuay them 0,5g axft humic bdt cd kfch thudc nhd hon 0,15mm.
Cho dung dich hdn hgp chay qua cot axft humic. Thu mdi phan doan 500ml de
dem di phan tfch ndng do kim loai bang phuang phap hap thu nguyen
tir.
16
2.5. PHUONG PHAP PHAN TICH KIM LOAI
2.5.1.
Phuang
phdp xdc dinh Pb(II)
Dixng
phuang phap chudn do Complexon vdi chi thi Xylen da cam.
De chuan do
true
tie'p
Pb^"^
trong dung dich axft cd the sir dung nhilu chat chi
thi khac nhau nhung d day chiing tdi sir dung Xylen da cam( ky hieu XO) pha vdi
KCI.
- Thudc thir:
+ Dung dich EDTA 0,01N
+ Dung dich dem axetat pH
=
5
+ Chi thi
XO/KCl
Phuang phap xac dinh: Trung hoa sa bd dung dich bang NaOH de'n pH
==
3 va
them 3ml dung dem axetat, khi dd dung dich cd gia tri pH la 5. Them vao mdt ft chi

thi va chuan do bang dung dich EDTA den chuyen mau tir tfm dd sang vang hoan
toan. Trong phuang phap chuan do nay ta can tranh ndng do dung dich dem axetat cao
vi khi dd diem tuong duang se khdng rd ret.
chiing tdi nhan thay phuang phap nay cd do nhay va do chfnh xac cao. Mat
khac ham lugng kim loai dugc nghien
ciiu
d day la
phii
hgp vdi phuang phap chuan do
complexon vi nhanh va re tiln. Vdi ham lugng kim loai nhd phai diing phuang phap
do phd ha'p thu nguyen tir.
2.5.2.
Phuang
phdp xdc dinh
Cd(II)
Dixng
phuang phap chuan do Complexon vdi chi thi Xylen da cam
Phep chuan do
true
tiep
Cd"""
vdi chi thi Xylen da cam tai pH
=
5 se gap phai
khd khan ve kha nang chuyen mau
ciia
chat chi thi tai diem tuang duang. Do dd phai
dung phep chuan do ngugc bang
Zn^^
.

17
PT
/
456'
2.5.3.
Phuang phdp xdc dinh Cu(II)
Phuang
phdp xdc dinh dong
bdng
phep chudn do complexon
'
Viec xac dinh nong do dong bang phuang phap chuan do complexon khdng
ma'y khd khan cho dii la chuan do true tiep hay gian tiep. Viec xac dinh ham lugng
Cu^"^
bang phep chudn do complexon cd the thuc hien trong khoang pH rat rgng vdi
cac chl thi khac nhau. Trong luan van nay tdi tien hanh trong mdi trudng axft yeu tai
pH = 5 va sir dung chi thi xylen da cam. Vdi ham lugng
Cu^""
dugc nghien ciru trong
cdng trinh nay thi viec ap dung phep chudn do complexon la rat td't.
2.5.4.
Phuang
phdp xdc dinh Zn(II)
Dixng
phuang phap chuan do complexon.
2.5.5.
Phuang
phdp phdn tich As
- Phuang phap xac dinh asen d dang asenomolipdat xanh
- Nguyen tac: As(V) tuang tac vdi amonimolipdat tao thanh axft

dj
da
asenomolipdic vang
H3[As(Mo30io)4],
rdi bi khir va chuyen thanh axft di da
asenomolipdic xanh thudng dugc ggi la xanh asenomolipdic cd cudng do mau xanh
ti
le vdi ndng do As. Nghien
ciiu
ky su tao thanh xanh asenomolipdic da chi ra rang khi
khir dang axft di da asenomolipdic vang xay ra hai qua trinh song song: tao xanh
asenomolipdic don gian va pha huy mdt phan xanh asenomolipdic. Cd the diing
hydrazinsunfat,
SnCl2,
hydroquinon, axft
asconic.
lam
chat khir.
Do do hap thu quang: Cue dai hap thu quang dang xanh asenomolipdic da khir
phu thudc vao chat khir sir dung. Do hap thu thudng dugc do d viing 700nm de'n
840nm. He sd hap thu phan tir
ciia
xanh asenomolipdic d 840nm la
2,5.10'"^.
- Thudc thir
-h
Dung djch chuan asenat: can
0,132g
AS2O3
rdi dem hoa tan trong 2 - 3ml

kilm
IN,
chuyen vao dinh
miic
100ml. Axft hoa bang HCl tdi phan
ling
axit.
Them
18
0,5g kaliclorat rdi pha loang tdi vach dinh
miic
lac dl dugc dung dich cd ndng do
Img
As/ml.
+ Amonimolipdat: Hoa tan
Ig
mudi amoni molipdat trong 100ml
H2SO4
giii
trong binh
polietylen.
+ Hydrazinsunfat: dung dich 0,15g/100ml.
- Quy trinh phan tfch
La'y 20ml dung dich mau mdi trudng trung tfnh chiia tii
1
de'n
50|a.g
As chuyen
vao binh 30ml. them vao 1ml amonimolipdat va 0,5ml dung dich hydrazinsunfat. Dat
binh len chau nudc sdi va giir 15 phiit ke tii

liic
nudc bat dau sdi trd lai. Sau dd lay cac
binh mSu
ra, lam lanh dudi vdi nudc va chuyen dinh
miic
25ml. Tie'n hanh do quang d
budc sdng 840nm, lap dudng chuan va tim nong do
ciia
As theo dudng chuan.
La'y nhung lugng chfnh xac As khac nhau vao cac cdc dugc danh sd va tie'n
hanh phan tfch bang phuang phap do quang xanh asenmolipdat tai budc sdng 840nm.
Ket qua thu dugc d hinh
2.1
dUdng
hap
thu quang
Hinh 2,1,
Du&ng
chudn do quang cua As
19
Thuc
i6
asen ton tai d hai dang
As(in)
va As(V). Phuang phap xac dinh asen
bang do quang d dang asenomolipdat xanh chi thuc hien dugc cho As(V). Vi vay, khi
xac dinh As(III)
cfc
phai dua As(III) len
As(V).Chiing

tdi chgn phuong phap dua
As(III) len As(V) bang nudc brom nhu sau:
La'y vao cdc 50ml dung dich As(III) cd ndng do
1
mg/ml, sau dd them tirng gigt
nudc brom lac tdi cd mau vang, de qua dem. Dun sdi nhe khoang 15 phiit, lam ngudi,
chuyen vao binh dinh
miic
250ml. Thu dugc dung dich As(V).
De chiing minh tfnh diing dan cua phuang phap tren tdi tien hanh pha dung dich
chudn asen tir hoa phdm
asenat-As(V)
dugc dung dich As(V) 1 mg/ml. Tie'n hanh len
mau asenomolipdat xanh sau dd do quang
ciia
hai dung dich tren lai budc sdng 840nm
ket qua dugc the hien d bang
2.1:
Bdng 2,1, Ket qud phdn
tich
so sanh giiia
[Asilllj-^BrJ vd
As(V) duac ten
mdu xanh asenmolipdat a budc song 840nm
As(V)
AS(lll)
JJ ^^^^
jy^
lgn ^^(V)
0,19

0,18
0,308
0,305
0,587
0,548
0,810
0,809
CHl/ONG
3.
K£T
QUA
vA
THAO LUAN
3.1 Nghien cuu kha nang hap gift cua axit humic ddi vdi
Pb^^
3.1.1.
Nghien
ci/u
dnh
hudtig
cua pH den khd ndng hdp giu
Pb^^
Axit humic la mdt axft yeu nen pH cd anh hudng manh den phan ling
ciia
axft
humic ddi vdi
Pb'.
De tim ra dilu kien pH tdi uu cho phan
ling
chiing tdi da khao sat vdi

dieu kien pH tiif
1 ^
6. Ket qua thu dugc nhu sau:
20
Bdng
3.1.
dnh hudng
cda
pH den khd ndng hdp
giU Pb
bdi axit
HAI
pH
Mphband4u(mg)
Npbc6nlai(mD/g)
Mpbc6nlai(mg)
Mpbbihipgia(mg)
NpbbihSpgia(mD/g)
1
40
0,19
39,31
0,69
0,003
2
40
0,16
32,55
7,45
0,04

3
40
0,14
29,00
11,00
0,05
4
40
0,09
18,72
21,28
0,10
5
40
0,07
15,29
24,71
0,119
5,5
40
0,08
16,00
24,00
0,115
6
40
0,06
11,40
28,56
0,14

M :
Ludng
Pb'*
bi hap
giur(mg)
0
8
pH
Hinh 3,1, dnh hudng cua pH den khd ndng hdp
giit
Pb^^
bdi Axit HAI
Ke't qua nghien
ciiu
kha nang hap
giii ciia
Axft Humic ddi vdi
Pb^'^cho
thay phan
ling rat tdt trong khoang pH tii 4,5 den 5,0. Tai khoang pH nay , vdi
lOOmg
axft humic
cd the ha'p giir tdi
24,71/40mg
Pb'""
va hieu suat hap
giir
dat 61,8% ham lugng
Pb^""
cd

21
trong dung dich. Nhung
d
pH
th^p
thi anh hudng rat
Idn
va kha nang hap giii cua axft
humic vdi kim loai nay giam
dk\,
^
Tuang tu
thf
nghiem nghien
ciiu
vdi
HAI
,
chiing
tdi
da khao
sat
anh hudng
ciia
pH den phan
ling ciia
HA2 vdi
Pb^"".
Ket qua thu dugc nhu sau:
Bang

3.2
anh hudng cua pH de'n phan
ling
cua axft humic HA2 vdi
Pb
2+
pH
Mpbbai,diu(mg)
Npbc6nlai(mDlg)
Mpba,nlai(mg)
Mphb.hipg.Q(mg)
Npbb,hipgi(r (mDlg)
1
40
0,19
38,5
1,50
0,007
2
40
0,16
32,55
7,45
0,04
3
40
0,13
27,80
12,20
0,06

4
40
0,09
19,50
20,50
0,10
5
40
0,08
15,70
24,30
0,12
5,5
40
0,08
15,60
24,40
0,12
6
40
0,06
12,50
27,50
0,13
E
M
: Luong
Pb^*
bj hap
giur(mg)

Hinh
3,2,
Anh hudng cua
pH
den phdn irng
cua axit humic HA2
ddi
vdi
Pb^^
22
Ket qua
ciia
bang 3.1
va
bang
3.2
cho thay kha nang phan
ling ciia
Pb^^
vdi
hai
loai axft humic
gSn
nhu
tuang duong nhau.Trong
qua
trinh nghien
ciiu
chiing
tdi chi

thuc hien dugc de'n
pH =
4,5-5,5.
Khi
mdi trudng
pH cao han
dung dich
Pb^""
se bi
thuy phan.
TCr
ket qua
tren
ta cd the
nhan dinh rang trong khoang
pH
tir
4,5
- 5,5 la
thfch
hgp cho kha nang phan
ling ciia
Pb^"*"
vdi axit humic
3,1,2, Nghien citu
dnh
hudng cua
th&i
gian den
khd

ndng hdp giit
De nghien
ciiu
anh
hudng
cua
thdi gian
de'n kha
nang
hap
giir
ciia
axft humic
vdi chi, chiing
tdi
tien hanh khao sat thdi gian phan
ling ciia
axft humic vdi
Pb^'^d
pH
=
4,5
tii
10 phiit de'n 360
phiit.Ket
qua thu dugc nhu sau:
Bdng
3.3.
Anh
hudng cua

th&i
gian
den
khd ndng hdp
giitPb^^
cua
HAI dpH ^
4,5
Thcri
gian (phut)
Mpbbandau(mg)
Cpbconla.
(mDlg)
Mpbconlai (mg)
Mpbbihapgia(mg)
Cpb
b,
hap
g.Q
(mDlg)
10
50
0,14
28,39
21,61
0,10
20
50
0,12
25,07

24,93
0,12
30
50
0,12
24,86
25,14
0,12
60
50
0,10
21,24
28,76
0,14
90
50
0,11
21,76
28,24
0,14
120
50
0,10
21,13
28,87
0,14
180
50
0,10
20,82

29,18
0,14
240
50
0,10
19,68
30,32
0,15
360
50
0,09
19,48
30,52
0,15
23