View Article Online

Analytical
View Journal

Methods
Accepted Manuscript

This article can be cited before page numbers have been issued, to do this please use: Y. Ma, Z. Tie, M.
Zhou, N. Wang, X. Cao and Y. Xie, Anal. Methods, 2016, DOI: 10.1039/C6AY00277C.

This is an Accepted Manuscript, which has been through the

Royal Society of Chemistry peer review process and has been
accepted for publication.

Accepted Manuscripts are published online shortly after

acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.

You can find more information about Accepted Manuscripts in the

Information for Authors.

Please note that technical editing may introduce minor changes

to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.

www.rsc.org/methods
 Page 1 of 9 Please do not adjust
Analytical margins
Methods

1
2
3 View Article Online
4
5
Analytical Methods DOI: 10.1039/C6AY00277C

6
7
8 ARTICLE
9
10
11
12 Accurate Determination of Low-level Chemical Oxygen Demand
13

Analytical Methods Accepted Manuscript

Using a Multistep Chemical Oxidation Digestion Process for
Published on 04 April 2016. Downloaded by University of California - San Diego on 05/04/2016 03:49:24.

14
15 Recei ved 00th Janu ary 20xx,
Accept ed 00th January 20xx
Treating Drinking Water Samples
16
17 DOI: 10.1039/x0xx00000x Yongjun Ma,* Zhenzhen Tie, Min Zhou, Na Wang, Xiaojuan Cao and Yun Xie
18
www.rsc.org/ An improved automatic potentiometric titration method for the determination of the low-level chemical oxygen demand
19
20 (COD) in drinking water was proposed and validated. In this method, a special digestion procedure that combines the
21 advantages of both alkaline potassium permanganate and acidic potassium dichromate digestion mode was adopted.
22 Under optimized operation conditions, the proposed method was successfully applied to determine the COD values of tap
23 water and marketable bottled water samples with satisfactory results. Specifically, the tolerable interference
24 concentration of chloride ions for a drinking sample was confirmed to be up to the level of 90 mg L -1 . Thus, for measuring
25 the low-level COD values of drinking water, the new method offered several technical characteristics that include high
26 degradation efficiency, good precision, less sampling volume (only 10.00 mL), short analysis time (about 25 min required
27 per sample), use of the mercury-free catalysts, a low detection limit (0.12 mg O2 L -1 ) and a broad linear range of COD
28 values (0.2-25.0 mg O2 L -1 ).
29
30 evaluati ng dri nking water quality.
31 Introduction According to the theoreti cal defini tion of COD, if al l
32 oxi diz abl e s ubsta nces i n a n aqueous sa mpl e ha ve been
At a ny gi ven ti me, the quali ty of dri nki ng water is of deep oxi diz ed to their hi ghest oxidati ve s tate i n the di gesti ve
33
concern, beca use i t is closel y rela ted to our dail y life a nd our rea cti on, f or exa mpl e, the exha usti ve oxidati on of hydrocarbon
34
35 heal th. Theref ore, to exa mi ne whether a vaila bl e wa ter compounds i nto ca rbon di oxide a nd wa ter, the ascertai ned
36 res ources meet the quality requirements f or drinki ng purpos es, COD values coul d be accepted as accurate i ndexes f or
37 many analytical techni ques for meas uri ng the chemi cal predicti ng water quality. However, when the complete
38 indexes of water quali ty rapi dl y a nd effecti vel y ha ve been degra dati on of all orga nic molecul es i n a n a queous sa mple is
39 developed.1 -2 In pa rti cul ar, chemical oxygen dema nd (COD) has not achieved, no matter what oxi da nt is us ed, the vali di ty of
40 been wi del y employed as a comprehensive para meter f or the the obtai ned COD would be ques tiona bl e. Thus, the chemi call y
41 quality ass ess ment of vari ous water s a mples .1, 3 -7 oxi dizi ng effici ency i n the s o- called wet oxi dati on di gesti on
42 Conventi onall y, since the COD val ues of unknown aqueous rea cti on acted on a water sa mpl es mus t pla y a key rol e on the
43 sa mpl es a re generall y defi ned with the f ound val ues from the accurate determi na ti on of COD.6
44 classical redox titrati on methods , in whi ch pota ssium Moreover, it is a known fact that the degra da ti on ra tio of
45 perma nga na te a nd potassi um dichromate are often chos en as oxi diz abl e s ubs ta nces basically depends on both the di gesti on
46 oxi da nts, two types of COD i ndexes, denoted by ei ther COD Cr mea ns a nd the oxi da nts used. For the pota ssium
47 or CODM n ha ve been esta blis hed. However, a s far as can be perma nga na te sta nda rd method, the i na ccurate meas urement
48 shown by the literatures, 1, 3-5 bas ed on the disti nct a nal yti cal of COD Mn f or a dri nki ng water sa mpl e is mai nl y ca us ed by the
49 properti es of the two sta ndard methods , CODCr is the lack of compl ete degra dati on to s ome oxi diza ble s ubs ta nces
50 preferred method for assessi ng the water quali ty in hea vil y under regula r experi mental conditi ons; 3 whil e for the
51 conta mi nated water bodi es, a nd CODM n is pref erred i n potassi um di chromate sta nda rd method, thei r a nal yti cal
52 relati vel y clea n water bodi es with low-l evel COD value (CODM n ca pa bility is s ubject to the poor a ccuracy f or the l ow COD
53 index les s tha n 5.0 mg O 2 L -1 ). In other words, the val ue of sa mpl e below a level of 5.0 mg O 2 L -1 ,1, 4-5 whi ch is really not
54 COD Mn would be the more reas ona ble index to use f or suita bl e for qua ntificati onall y determini ng typi cal COD val ues
55
of dri nki ng wa ter as low as 3 mg O2 L -1. 2 Theref ore, to remedy
56
the s ome defici encies of the two existi ng s ta ndard COD
57 *Key Laborato ry of Bioelectrochemist ry and Environmental Analysis of Gansu
Province, College of Chemistry & Chemical Engineering , No rthwest No rmal indexes f or the titrati on determi nati on of l ow-level COD val ues
58
Universit y, L anzhou, 730070, P. R. China in dri nking water sa mpl es, we have deci ded to purs ue a more
59 E-mail: mayj@ nwnu.edu.c n; Tel: (086-0931) 7970806
accurate COD index by usi ng si gnifica ntl y i mproved di gesti on
60 †Electronic Sup plementary Info rmation (E SI) avai lable: See
DOI: 10.1039/x0x x00000x techni ques.

This journal is © The Royal Society of Chemistry 20xx Anal .Met hod s, 2016 , 00, 1 -3 | 1

Please do not adjust margins

 Please do not adjust margins
Analytical Methods Page 2 of 9

1 Analytical Methods ARTICLE

2
3 Over the pas t decades, wi th the devel opment of i nnovati ve more s ensiti ve a nd a ccurate method f or the low-level COD
View Article Online
4 di ges ti on techni ques a nd detecti on i nstruments, several ra pi d DOI:
determi nati on i n dri nking water still needs to10.1039/C6AY00277C
be devel oped.
5 methods for COD determi na ti on, such as a ra diati on-assis ted In this study, we utilize the adva nta ges of both the al kali ne
6 di ges ti on method, 8-10 a photoelectroca tal ytic degra dati on potassi um perma nga na te a nd a ci dic potassium dichromate
7 method,1 1-13 a photocatal yti c oxidati ve degra dati on method, 7, methods to contrive a new di gesti on mode f or treati ng
14-15
8 a n el ectrochemical oxi dati on method, 16 -2 0 flow i njecti on aqueous sa mpl es a nd have s uccessf ull y es ta blished a
9 anal ysis 21 -24 a nd s pectrophotometry,25 -2 6 als o have ma de much practi ca ble potenti ometri c titrati on method that exhi bits the
10 progress . However, unf ortuna tel y, none of these techniques excellent anal ytic properties needed for l ow-level COD
11 are perf ect for the determi nati on of low-level COD dri nki ng determi nati on in dri nki ng water. Beca use of its hi gh
12 wa ter sa mples so fa r. For i nsta nce, Li a nd co- worker
15
ha ve degra dati on effici ency, good precisi on a nd l ow li mit of
13

Analytical Methods Accepted Manuscript

attempted to us e a photocatal ytic oxidati ve degra da tion a cti on qua ntificati on (LOQ), we hope this method ca n provi de a more
Published on 04 April 2016. Downloaded by University of California - San Diego on 05/04/2016 03:49:24.

14 on TiO2 photoca tal yst to degra de organi c poll uta nts, and to credi ble COD index f or the quality assess ment of dri nki ng
15 couple with the sensi tive fluorescence meas urements of Ce3 + wa ter.
16 ion to qua ntif y the COD load i n a quati c sa mples . Whereas the
17 method tha t hol ds a detecti on li mit (0.9 mg O2 L -1 ) a nd a linear
18 ra nge of COD val ues (0-100.0 mg O 2 L-1 ) has been merel y Experiments section
19 applied to the COD i n la ke wa ter a nd si mulate s ewa ge sa mpl es,
20 but does not vali da te the feasi bility f or measuri ng dri nki ng
Materials and reagents
21 7 All chemi cals us ed were analytical gra de or hi gher grade
wa ter sa mpl es. Moreover, Akhoundza deh a nd co- worked als o
22 quality (s uch as gua ra nteed rea gent gra de), a nd all of them
ha ve reported on a green method f or the qua ntitati ve
23 were used without a ny f urther purifica tion. Hi gh- purity
determi nati on of l ow COD values of a queous sa mpl es, whi ch
24 dei onized wa ter (18 MΩ cm) was us ed through all of the
invol ves to UV-i nduced oxi dati on di gesti on with hydrogen
25
peroxi de as a n assis ta nt oxidant. However, the practical resul ts experi ments.
26
in their experi ments shows that the reported method ca n The stock sol uti ons of potassi um perma nga na te (KMnO4 ),
27
factuall y determi ne three drinki ng waters (ta p water, mi neral potassi um dichromate (K 2 Cr 2O 7) a nd ferrous a mmonium
28
wa ter and s pri ng wa ter) jus t in the detecti on ra nge of 10-18 sulfate ((NH 4) 2 Fe(SO4 )2 , FAS) were prepared as des cri bed i n the
29
mg O2 L -1, rather tha n in the domain of a low-level COD. standa rd methods. 1-4 Details of the prepa rati on of the catalys t
30
Therefore, although thes e methods ha ve demonstrated ma ny sol uti ons a nd the standa rd sa mpl e s olutions were provi ded i n
31 †
32 adva nta ges over the sta ndard ti tra ti on methods, incl uding the ESI. Beca use of its recognized theoreti cal COD val ue,
33 direct acquisiti on of a nal yti cal si gnals a nd the ra pi dity of the potassi um hydrogen phthal ate (KHP) was a pplied as a probe
34 anal ysis, bas ed on the reported evi dences, we concl ude tha t standa rd compound to a pprais e the vali dity of the
35 the relia bility of these new methods ma y be not enough to experi mental resul ts in this study. A sta nda rd sa mple of KHP
-1
36 achieve our sa tisfaction f or practi cal a pplica tion to a l ow-level wi th the theoretical COD val ue of 10.0 mg O2 L was prepa red
37 COD drinki ng water nowa da ys. Furthermore, if there was no by a ppropria te dil uti on of KHP stock s ol uti on pri or to us e.
38 verifica ti on of a more accura te COD i ndex by usi ng the
39 standa rd ti tra ti on methods , thes e techni ques mi ght not be Apparatus
40 approved by a ny offi cial a gencies for the routi ne a nal ysis of The experi mental equi pment us ed i n this study comprised of a
41 the real dri nking water sa mples. glass refl ux device and a n automa tic potenti ometric titrator
42 On the other hand, the incessa nt eff ort als o has been tha t was connected to an electrochemi cal workstati on. The
43 made to improve upon the classi cal titrati on methods for COD refl ux device consisted of a 250 mL ground- glass neck coni cal
44 determi nati on by combi ni ng the a utomati c potenti ometri c flask a nd a 40 cm l ong s pherical condens er pi pe . A constant
45 titra ti on method wi th the more effici ent di gesti on temperature ma gnetic stirrer (85- 2, Sha nghai , China) was used
46 techni ques. 27 In a dditi on, though the use of ra diati on-assis ted for heati ng a nd sti rri ng, a nd a n automati c potenti ometri c
47 di ges ti on methods has s ome safety ris ks, the powerf ul titra tor (ZD-2, Sha nghai, China ) was us ed to conduct the
48 di ges ti on techni ques like as mi crowave (MW) a nd ul tras ound potentiometri c ti tra tion. The potenti ometric curves were
49 (US) ra dia ti on assis ta nt methods to be a ppli ed in the sa mpl e recorded usi ng the open ci rcuit potential mode of the
50 pretrea tment process of COD determi nati on i ndeed hel p to electrochemi cal worksta ti on (CHI610, Shanghai Chenhua
51 increa se the oxi dizing effici ency a nd shorten the a nal ysis Instrument Co. Ltd., Chi na ). The two-el ectrode s ystem was
52 8
ti me. With this techni que, we ca n ha ndil y execute the compos ed of a Pt f oil i ndi cati ng electrode a nd a sa tura ted
53 potentiometri c ti tra tion operati on usi ng a sta nda rd s ol uti on of
54 calomel ref erence electrode (SCE) i ns erted into a titrati on cell
a reduci ng rea gent a nd calculate the COD val ue of the a queous wi th a Na2 SO4 (1.0 M) salt bri dge.
55 sa mpl es with hi gher a ccuracy a nd lower cos t. Nevertheles s,
56
even usi ng these f easi ble methods , we ha ve still fa ced with Experimental procedure
57
many difficul ties tha t i ncl ude the i nsta bility of meas urement
58 As s hown i n Scheme 1, every a queous sa mpl e wa s di ges ted
operati on, the i nevitabl e us e of toxic mercuri c salt, a li mi ted
59 wi th a chemicall y oxi dati ve process in which there was one
linea r ra nge and the inf eri or sensi ti vity. Theref ore, a si mpler,
60 di ges ti on s tep performed in al kaline media and a s econd in

This journal is © The Royal Society of Chemistry 20xx Anal . Method s, 2016 , 00, 1-3 | 2

Please do not adjust margins

 Please do not adjust margins
Page 3 of 9 Analytical Methods

1 Analytical Methods ARTICLE

2
3 View Article Online
4 where V0e p a nd V ep (mL) ref er to the termi DOI:nal10.1039/C6AY00277C
tit rati on vol ume
5 of FAS f or the bla nk sa mple and the real a queous sa mpl e,
6 res pecti vel y. The termi nal titrati on vol ume of FAS can be
7 identifi ed as the end- point volume by the fi rst deri vati ve plot
8 of the recorded potenti ometri c curve, cF AS is the concentrati on
9 of f errous a mmoni um s ulfate s ol uti on (M), and Vs is the
10 sa mpli ng vol ume of the aqueous s a mple (mL). Beca use the
11 Scheme 1 Schema tic dia gra ms of the sequential experi mental val ues of V0e p, V ep, cF AS a nd Vs ca n si mpl y be obtai ned f rom
12 procedures. experi mental data, the accuracy of COD meas urement i n the
13

Analytical Methods Accepted Manuscript

presented method could be eval ua ted by compari ng the
Published on 04 April 2016. Downloaded by University of California - San Diego on 05/04/2016 03:49:24.

14 acidi c media, a nd afterward a fi nal ba ck-titrati on s tep was calculated COD val ues a gai nst the theoretical COD val ues of
15 perf ormed on the treated aqueous sa mpl e to quantita tivel y the sa me KHP standa rd sa mpl es.
16 calculate COD. In detail , we firs t tra nsferred 10.00 mL a queous
17 sa mpl e sol ution i nt o a 250 mL ground- glass neck coni cal flas k,
18 added the al kali ne di gesti on sol uti on which consis ted of 4.50 Results and discussion
19 mL KMnO4 (5.00 mM), 0.90 mL MnSO4 (10.0 mM), 3.30 mL
20 NaOH (50 mM) a nd 0.25 mL K2 S 2O 8 (10 mM), then heated to a
Optimization of digestion reaction time
21 In the case of the tra diti onal sta nda rd method for the
gentle boil for several minutes (t 1 ) under open-reflux a nd
22 determi nati on of CODM n or COD Cr, the oxi da ti ve di gesti on
ma gneti c sti rring conditi on. Once the opti miz ed di ges tion ti me
23 rea cti on of a n a queous sa mpl e is ca rri ed out by usi ng one of
(t 1 ) was rea ched, the second, a ci dic di ges ti on s tep woul d be
24 the strongest oxi dizi ng a gents , such as KMnO 4 or K 2 Cr 2O7 .
carried out on the sa me aqueous sa mpl e. Specificall y, this s tep
25 However, when the degra da tion effi ciency of the standa rd
wa s perf ormed as foll ows: after firs t heati ng was s topped a nd
26 sa mpl e is verifi ed by ta king the ra ti o of the calcula ted COD
the refl ux device was disconnected tempora ril y, a ppropriate
27 val ues versus the theoreti cal COD of the KHP compound i n the
28 a mounts of water and the aci di c di gesti on sol uti on were
present s tudy, our pri ma ry experi mental outcome has
29 poured i nto the coni cal flas k contai ni ng the pri maril y di ges ted
demons tra ted tha t when use of a ny one si ngle oxi da nt, s uch as
30 sa mpl e s olution, and kept the total volume of the mi xi ng
KMnO 4 and K2 Cr2 O7, the degra dati on ra tio of the KHP
31 sol uti on to a bout 30 mL by a dding a few milliliters of
compound does not reach 100% wi thin the s hort di gesti on
32 hi gh-purity water. Here, the a cidi c di gesti on s ol uti on consis ted
ti me a bout 15 mi n. Thus, it is practical to contrive the two
33 of 2.40 mL H2 SO4 (9.0 M), 2.25 mL K2 Cr2 O7 (5.00 mM), 0.90 mL
types of oxi da nts at one ti me to increas e the total degra dati on
34 CuSO 4 (10.0 mM) a nd 0.90 mL Ag2 SO4 (7.5 mM). After tha t, the
rati o of the orga nic matter i n a di gesti on rea cti on a nd obtai n a
35 coni cal flask was sha ken sli ghtl y to ma ke the sol uti on
lower li mi t of COD detection f or the a queous sa mple. As
36 homogenous a nd was di ges ted a gai n f or heati ng s everal
shown i n Scheme 1 in the experi mental secti on a bove, we
37 mi nutes (t2 ) under the sa me opera ti on condi ti ons jus t
ha ve ela bora tel y desi gned a novel di gesti on mode f or COD
38 menti oned. Once the entire di gesti on process was compl eted,
determi nati on in dri nki ng water a nd prove its superi ority
39 we disconnected the reflux condens er, cool ed the conical flas k
herei n as a novel di gesti on mea ns by combi ni ng the
40 to room temperature naturall y a nd tra nsf erred all of the
adva nta ges of both the al kali ne potassium perma nga na te a nd
41 di ges ted s ol uti on into a 250 mL bea ker. Fi nall y, excess oxidants
acid potassi um dichromate method.
42 at pres ent were titrated by 3.00 mM FAS as the potenti ometri c
43 To s tudy the ca pa bility of this novel method, a series of
curve was si mul ta neousl y recorded, f rom which the end- point
44 opti mizi ng tests i nvol vi ng the a dded a mount of oxi da nts a nd
volume of the titrant was ascertai ned. Because the
45 catal ysts, the open- refl ux ti me a nd the aci dity of the di gesti on
experi mental conditi ons were sli ghtl y different f or the every
46 media ha ve been performed carefull y. Fi g. 1 s hows the
batch of water sa mpl es, the titri metric end-poi nt volume for a
47 va riati on of degra da tion effici ency wi th i ncreas e of the
bla nk sa mple was ta ken under the sa me experi mental
48 open-refl ux ti me. When setti ng the open- refl ux ti me t 2 to a
conditi ons to deal with a real a queous sa mpl e.
49 cons ta nt val ue of 5.0 mi n duri ng a cidi c di ges tion process , as
50 seen in Fi g. 1A. Then, it can be observed tha t the degra dati on
Calculation
51 efficiency of the KHP s ta ndard s ubsta nce si gnifi ca ntl y i ncreas es
According to the pri nci pl es of the redox ba ck- titrati on method,
52 and reaches a platea u regi on at a pproxi ma tel y 100%
there is a certain stoichi ometric rela ti ons hi p between the
53 degra dati on rati o as the open- refl ux ti me t 1 is i ncreas ed duri ng
a mount of oxi da nt remai ned a nd the a mount of reducti ve
54 alkali ne di gesti on proces s. These evidences affi rm the
titra nt added, which ma y be determi ned from the end- point
55 volume of FAS cons umed i n titrati on reacti on. Consi deri ng tha t
powerf ul oxi da tive capabili ty of al kali ne pota ssium
56 perma nga na te for the di gesti on of speci es i n aqueous sa mpl es
only one el ectron is tra nsferred i n the Fe2 + /Fe3 + couple, the
57 and als o indi cate the opti mal val ue of t 1 is 8.5 min.
COD value ma y be cal cul ated usi ng the f oll owi ng equa ti on: 1, 4,
58 28 Compa rati vel y, when holdi ng t1 a t 8.5 mi n, as seen i n Fi g. 1B,
59 (V0  V ep )  c FAS  8000
ep
we find tha t there is a n i nitial as cending curve segment a nd a
60 COD (mg O2 L-1 )  maxi mum degra dati on ra tio of a pproxi ma tel y 100% a t the
VS

This journal is © The Royal Society of Chemistry 20xx Anal . Method s, 2016 , 00, 1-3 | 3

Please do not adjust margins

 Please do not adjust margins
Analytical Methods Page 4 of 9

1 Analytical Methods ARTICLE

2
3 compl ete di gesti on of the standa rd sa mples and Online
View Article no
4 unfa vora ble thermal decompositi on of KMnO DOI: 10.1039/C6AY00277C
4. With this novel
5 di ges ti on method, the total ti me requi red f or the di gesti on of
6 each s a mple will be less tha n 15 mi n. This is a quite s hort ti me
7 compared to the 30 mi n required f or the conventional COD M n
8 method.3 Based on the experi mental res ults, it is can be
9 deri ved that the use of a combi nati on of the two oxidants
10 provi des a hi gher degra dati on effici ency compa red with either
11 of the oxi da nts i ndivi duall y. Las tly, it is worth noti ng that the
12 sequence of two di ges tion processes mus t be occurred i n the
13

Analytical Methods Accepted Manuscript

order descri bed: the first di gesti on sta ge conducted in alkaline
Published on 04 April 2016. Downloaded by University of California - San Diego on 05/04/2016 03:49:24.

14 di ges ti on medi a, a nd the s econd di gesti on sta ge done in a cidi c

15 di ges ti on medi a. If the order was reversed, it woul d res ul t in
16 compli cati ons in the s ubs equent ba ck-ti tra tion process. For
17 exa mpl e, the preci pitati on of the metal hydroxi des whi ch
18 formed f rom s ome of the metal i ons a dded as di gesti on
19 catal ysts (Mn2 +, Cu 2+ and Ag + ) woul d ma ke the process of
20 titra ti on more difficult. Besi des, si nce the ba ck- titrati on
21
operati on must be ca rri ed out i n a ci dic s ol uti on, the desi gned
22
di ges ti on procedures for trea ting the aqueous sa mple will be
23
more reas ona ble tha n that by the revers e opera tion s equence.
24
25
Selection of catalysts
26
As we all know, some metal i ons when a dded as di gesti on
27
28 catal ysts 29 ha ve a key i nfl uence on the di gesti on reacti on of the
29 aqueous sa mple a nd may s hortened the di gesti on ti me a nd
30 enha nce the degra da ti on effi ciency greatl y. Accordi ng to s ome
31 Fig. 1 Vari ati onal trends of the degra da tion effici ency f or a KHP litera tures,3 0-32 it ca n be known that MnSO 4 gi ves ris e to a cti ve
32 standa rd sa mple a nd the e nd- point vol umes of FAS cons umed manganese oxi des a nd trivalent ma nga nes e speci es i n al kali ne
33 for a bla nk sa mpl e ha ve dependence on the open- refl ux ti me conditi ons, whi ch ca n then a ct as an a vaila ble di gesti on
34 at the boili ng tempera ture of di gesti on sol ution i n the alkaline catal yst. In additi on, the bas ed-activated pers ulfate, acted as
35 di ges ti on process (A) a nd i n the a ci dic di ges ti on process (B), an as sisted oxi dati on rea gent but not a ca tal yst herei n, als o
33 -3 5
36 res pecti vel y. generates mul ti ple rea cti ve s pecies , incl udi ng s ulfa te a nd
37 hydroxyl ra dicals tha t ha ve the ca pa bility of oxi dizing s everal
38 ti me t 2 of 5.0 mi n f or the KHP compound. This provi des direct types of a romati c ri ng compounds. 36 Thus , we still chose to
39 proof that there certai nl y exists a cooperati ve di gesti ve a cti on add MnSO4 a nd K2 S 2O 8 as common ca tal ysts in the alkaline
40 between the al kali ne potassi um permanganate a nd a cidi c di ges ti on s ol uti on to enha nce the di gesti on of orga ni c
41 potassi um dichromate method f or the wa ter sa mpl e compounds.3 7 In this ca se, it ca n be obs erved tha t the alkaline
42 treatment process. di ges ti on s ol uti on al wa ys remai ns a trans pa rent dark red col or,
ep
43 Furthermore, the a pparent vari ati on of V 0 , the termi na l but it does not turn green in presence of plentiful K 2 MnO4 nor
44 titra ti on volume of FAS for a bla nk sa mple is dis cussed herein. does any brown preci pitate deri ved from MnO 2 f orm.
45 As s hown i n Fi g. 1, the ti me t2 ca n si gnifica ntly affect the val ues Therefore, we can a ssume tha t thes e active ca tal yti c speci es
46 of V0e p, a nd affects them more tha n ti me t 1 does. When t2 is (MnO 2, Mn3 +) react ra pi dl y with the orga nic s ubstances i n the
47 over 6.0 mi n, the degra dati on efficiencies of KHP a nd V0e p aqueous s a mple and the mai n reducti ve product of KMnO 4 is
48 decrease si multa neousl y, i n s uch a wa y that the s toichi ometri c Mn2 +.
49 relati ons hi p in the back- titrati on process must be destroyed, In the s econd a cidi c di gesti on process, we utilize Ag2 SO 4
50 and the theoretical equa tion gi ven a bove f or cal cul ati ng COD and CuSO 4 as the common catalys t, i n whi ch Ag 2 SO 4 not onl y
51 val ues becomes ina pplicabl e. Moreover, beca us e a s mall promotes the di gesti on of s a mples but als o prevents the
52 a mount of brown sedi ment of MnO2 is occasionally observed interf erence of chlori de i ons i n the di ges tion to s ome extent,
6,

53 in the cool aci di c di ges tion sol ution under the actual operati ng 38
while the catal ytic a cti on of CuSO 4 has al rea dy been known
54 conditi ons, we deduce that the reas on for this situati on ma y in ca tal yti c wet oxi dati on process es. 2 9 Certai nl y, beca use the
55 be the thermal decompositi on of resi dual KMnO 4 l eft over acidi c di gesti on process is s tarted jus t after the al kaline
56
from the alkaline di gesti on process when heati ng the a cidi c di ges ti on process is complete d, the remai ni ng oxi da nt a nd
57
di ges ti on s oluti on just i n the pres ence of K2 Cr 2O 7. Hence, the catal ysts will tra nsfer i nto the aci di c di gesti on s ol uti on. When
58
full oxi da ti ve degra da ti on of the KHP compound is ess entiall y the aci di ty of the di gesti on s olution is enha nced, we will
59
achieved by the opti mized al kali ne di gesti on ti me t1 of 8.5 mi n convert the remai ni ng manganese s pecies (K2 MnO4, MnO 2 a nd
60
and a cidi c di ges ti on ti me t2 of 5.0 mi n, whi ch ens ures the Mn3 + ) with hi gh oxi dati on states to MnO 4 - a nd Mn2+ i on

This journal is © The Royal Society of Chemistry 20xx Anal . Method s, 2016 , 00, 1-3 | 4

Please do not adjust margins

 Please do not adjust margins
Page 5 of 9 Analytical Methods

1 Analytical Methods ARTICLE

2
3 through the dis proportiona ti on rea cti on, a nd K 2 S 2O8 to s ulfate View Article Online
4 ion a nd oxygen gas wi th the thermo- hydrol yzed reacti on i n a DOI: 10.1039/C6AY00277C
33
5 gentle boil di gesti on s ol uti on. Actuall y, when addi ng the
6 acidi c di ges tion rea gent, which contai ns dil ute s ulfuric a ci d,
7 CuSO 4 a nd Ag2 SO4, i nto the di gested al kali ne sa mpl e s ol uti on,
8 no dis tinct col or cha nge has occurred. To determi ne the
9 appropriate a dditi on a mounts of the di ges tion ca tal ysts , we
10 ha ve opti miz ed not onl y the a mounts of ea ch catal ys t but als o
11 the correlati ng mol ar proporti on (see the Fi g. S1 a nd S2 f or
12 †
detail i n ESI). Fi nall y, it is i mporta nt to stress here a gai n tha t
13

Analytical Methods Accepted Manuscript

the di ges ted a ci dic s a mple sol ution ca n be directl y ta ken to
Published on 04 April 2016. Downloaded by University of California - San Diego on 05/04/2016 03:49:24.

14 operate the a utoma tic potenti ometri c ti tra tion without a ny

15 adjustment of its aci dity. In this condi tion, when a dding FAS
16 into the bea ker contai ni ng the treated sa mple s oluti on, the
17 col or of the sa mpl e s ol uti on gra duall y cha nges f rom da rk red
18 to li ght brown and eventuall y to light green (due to the bul k Fig. 2 Effects of the chl oride ion concentra ti on on the COD
19 formati on of Fe2+ i on). Thi s evi de nce i ndicates that the us e of val ue i n a s yntheti c KHP s ta ndard s a mple (with COD val ue of
20 these ca tal ysts ha ve no unfa vora bl e i mpa cts on the actual 10.0 mg O2 L-1 ) contai ni ng the diff erent a mounts of chl oride
21
titra ti on proces s. ion.
22
23
Interference of chloride ion enough to oxi dize a si gnifi ca nt a mount of chl ori de i on; (3) the
24
Beca us e chl oride ions ca n be oxi diz ed to chl ori ne by strong sulf uri c aci d concentrati on (a bout 0.7 M) is low i n the mi xed
25
oxi dizi ng a gents a nd ca n res ult a posi tive error in the COD di ges ti on s oluti on contai ni ng KMnO 4 and K 2 Cr 2O 7, a nd (4)
26
determi nati on,5 both the conventional CODCr a nd CODM n there is the mas k effect due to good coordinati on a bility of Ag +
27
28 indexes s uff er f rom the interference of chl ori de i on. 3 -5 The and Cr 3+ to chlori de i on; 6, 2 6, 39 so that onl y a s mall a mount of
29 present means es ta blis hed f or eli mi na ting the interference of chl oride i on is qua ntitati vel y oxi diz ed to chl ori ne. Hence, the
30 chl oride is the a ddi ti on of mercury (II) sulfa te a nd/or sil ver proposed method is s uita ble f or the determi na tion of l ow-level
31 sulfate to compl ex it a nd thus prevent i ts oxi da ti on. 8, 39 Thus, COD i n dri nki ng wa ter sa mples except thos e ta ken f rom
32 the interf erence due to chl oride ions is studi ed by addi ng brackis h wa ter s upplies .
33 chl oride i ons i n va rious a mounts i n the range of 0-800 mg L-1
34 to the KHP standa rd sa mple under the opti miz ed operati on Validation of the method
35 conditi ons. The res ults , as s hown i n Fi g. 2, i ndica te that the Automati c potenti ometric titrati on techni que allows the COD
36 COD val ue of the KHP sta nda rd sa mpl e is not aff ected by meas urement more ra pi d a nd ma kes the experi ment
37 chl oride ion bel ow the concentra tion level of 90 mg L -1 , whi ch operati on more convenient as a routi ne a queous sa mpl e
38 ca n cover the representa ti ve l evel of normal chl oride i on anal ysis method. The potenti ometri c ti tra tor is connected with
39 concentrati ons f ound i n ta p wa ter. 4 0 However, when the a sof twa re- controlled electrochemi cal worksta ti on , ma ki ng i t
40 concentrati on of chlori de i on is over 200 mg L-1, it can be fi nd eas y to coll ect the potenti ometri c curves f or ea ch titrati on
41 tha t the COD val ues of the KHP sta nda rd sa mpl e rise steepl y process i n real ti me (Fi g. 3A). For instance, the i nset i n Fi g. 3A
42 wi th the concentrati on of chl oride ion i n the ra nge of 200- 800 shows the potenti ometri c curve a nd its firs t deri va tive curve
-1
43 mg L , and a local li near regres sion equati on which has a sl ope for a real titra ti on of the KHP sta ndard sa mple. From the
44 of 0.0096 a nd a correla tion coeffici ent of 0.9982. In theory, if abs cissa of the pea k poi nt, we coul d ascertai n the end- point
ep
45 the chl ori de i on were chemi call y oxi dized to chl ori ne, the volume of FAS (V , mL) f or ea ch titrati on process a nd calculate
46 theoretical COD val ue contributed from chl oride ion woul d be the COD val ue of the aqueous s a mple.
47 the equi val ent of 0.226 mg O 2 L-1 for the pres ence of every 1.0 Further work is perf ormed to validate the formula us ed f or
48 mg L-1 chl ori de ion, rather tha n the slope of 0.0096 obtai ned calculati ng COD values under the back-ti tra tion conditi ons i n
49 from our experi ment whi ch has over 20 ti mes l ess tha n the the di gested mi xi ng s oluti on contai ning the excess oxi da nts of
50 expecta ti on val ue . Theref ore, thes e resul ts reveal that the KMnO 4 and K2 Cr2 O7. Under the opti mized experi mental
51 additi on of Ag+ eli mi na tes the i nfl uence of chl ori de i on to a conditi ons, the cali brati on curve (Fi g. 3B) has been obtained, i n
52 quite extent, a nd the COD supplied due to exis ti ng low whi ch the theoreti cal COD val ues of a s eri es of KHP standa rd
53 concentrati on of chl ori de i on can be i gnored when mea suri ng sa mpl es a nd the differences between a pai r of end- point
54 COD val ues in a normal drinki ng wa ter sa mpl e. volumes of FAS exha usted for a bla nk and s ta ndard sa mpl es
55 As a res ult, when treati ng a a queous sa mple by thi s (△V=V 0e p - Ve p ) ha ve a good li near rel ati onshi p over the ra nge
56
di ges ti on mode, the wea kened i nterf erence of chl ori de ion ca n of 0.2- 25.0 mg O2 L -1 . After a nal yzi ng the regressi on equati on,
57
be explai ned as a combi na ti on of f our fa ctors: (1) the much we ca n determi ne tha t the cali brati on curve sl ope of 2.4173 is
58
shorter di ges tion ti me does not all ow enough ti me f or the side in a greement wi th the sl ope cal culated by the f ormula
59
rea cti on of the oxi da nt with chl oride to progress ; (2) the cFAS ×8000/Vs. This evidence a dequately proves tha t when usi ng
60
oxi da ti ve capa bility of KMnO 4 i n al kali ne media is not strong the propos ed method, the stoi chi ometric rela ti ons hi p i n the

This journal is © The Royal Society of Chemistry 20xx Anal . Method s, 2016 , 00, 1-3 | 5

Please do not adjust margins

 Please do not adjust margins
Analytical Methods Page 6 of 9

1 Analytical Methods ARTICLE

2
3 View Article Online
4 DOI: 10.1039/C6AY00277C

5
6
7
8
9
10
11
12
13

Analytical Methods Accepted Manuscript

Published on 04 April 2016. Downloaded by University of California - San Diego on 05/04/2016 03:49:24.

14
15
16
17
18
19
20 Fig. 4 Regressi on tes ts compa ri ng the meas ured COD a nd
21
theoretical COD val ues of some indi vi dual orga nic compound
22
sa mpl es or thei r mixture sa mples containi ng KHP, glucose a nd
23
gl yci ne.
24
25
standa rd s ubsta nces were determi ned a nd compared with
26
their theoretical COD val ues. As seen i n Fi g. 4, f or vari ous
27
28 concentrati ons of KHP, gl ucose, gl ycine, a nd thei r mi xtures, the
29 COD val ues obtai ned from the proposed method were found
30 to be i dentical to the corres pondi ng theoreti cal val ues, and the
31 slope and correl ati on coefficient were 1.0030 and 0.9996 i n
32 the ra nge of 0.5-25.0 mg O 2 L -1, res pecti vely. Thes e resul ts
33 indica ted that the proposed method was ca pa ble of oxi dizi ng
34 different compounds unif orml y a nd ens ured the complete
35 oxi da ti on of the tes ted compounds.
36 Fig. 3 The potenti ometri c curves of a series of KHP standa rd Furthermore, the propos ed method has been a ppli ed to
37 sa mpl es wi th different theoretical COD val ues (A), in which the meas ure of a real dri nki ng water sa mpl es, a nd the obtai ned
38 gra ph a-h repres ents COD values of 0.0, 1.0, 2.0, 5.0, 10.0, 15.0, res ults are listed in Ta ble 1. Thes e dri nki ng wa ter sa mpl es
39 20.0 and 25.0 mg O 2 L -1 , res pecti vel y. Ins et i n the dia gra m (3A) were coll ected f rom tap wa ter nea r our la b a nd f rom the
40 illustrates the as certai nment wa y of end- poi nt vol ume (Ve p ) different bra nds of bottled drinki ng water. Three repeati ng
41 upon a curve (g). And, the regressi on curve between △V val ues meas urements were perf ormed f or ea ch sa mpl e. It is found
42 and its theoretical COD val ues of s ome KHP s ta ndard sa mpl es tha t the mea n COD values of ta p water sa mpl es are i n the
-1
43 is dra wn (B). ra nge of 3.00- 3.50 mg O2 L a nd those COD val ues of bottled
44 wa ter sa mpl es a re of 0.2 5-0.60 mg O2 L -1. By all a ppea ra nces,
45 ba ck- titrati on calcula tion f ormula is still tena ble, a nd it ma y be the determi ned COD of the ta p water sa mple is much hi gher
46 trusted to provi de a hi ghly accurate COD val ue. The pres ent tha n a ny one of the commercial bottled water sa mpl es, a nd
47 accuracy has vali dated by a rela tive mea n errors of 1.08% (n=3) thos e values of s ome bottled waters als o a re as l ow as 0.30 mg
48 for a KHP s ta ndard sa mple with theoreti cal COD of 0.50 mg O 2 O2 L -1, whi ch ma y achieve the COD requirement of the mos t
49 L-1 . Moreover, the detecti on li mit of this method that ca n be strict wa ter quali ty security s ta ndards f or a fine dri nki ng wa ter.
50 represented by a cal cul ati on f ormula (3σ/s) is obtai ned as 0.12 Here, the avera ge recoveri es were exa mi ned by a ddi ng
51 mg O 2 L-1. Here, σ is the standa rd devia ti on of V 0e p as obtai ned potassi um hydrogen phthalate, phenol a nd gl ucose into the
52 from 12 repeati ng tes ts f or the sa me bla nk sa mpl e a nd s is the real a queous s a mples , res pecti vel y. The a vera ge recoveries are
53 slope val ue of calibra tion curve. in the ra nge of 94.0% to 100.7%, whi ch ca n f ull y satisf y the
54 requirement of practi cal a nal ysis. In a dditi on, to exa mi ne the
55 Application to standard samples and real samples precisi on of the COD meas urements, we also ha ve eval ua ted
56
To demonstrate the practical a pplicati on of this method for their confi dence i ntervals a t a level of 0.95 and determi ned the
57
more complex sa mpl es, we ma de the testi ng experi ments f or RSD by performi ng three parallel detections on each sa mple.
58
va rious s yntheti c aqueous sa mpl es that consisted of several As seen i n Tabl e 1, thes e res ults a re a ccurate enough to trus t
59
representati ve s ta ndard compounds incl uding KHP, gl ucos e our new method to gi ve the COD i ndex f or common dri nki ng
60
and gl yci ne 9, 1 3, 1 8 or thei r mi xtures. The COD val ues of these wa ter sa mpl es a nd to provi de a more s uita bl e method f or

This journal is © The Royal Society of Chemistry 20xx Anal . Method s, 2016 , 00, 1-3 | 6

Please do not adjust margins

 Please do not adjust margins
Page 7 of 9 Analytical Methods

1 Analytical Methods ARTICLE

2
3 View Article Online
4 Table 1 Measurement resul ts of the COD in the real wa ter samples DOI: 10.1039/C6AY00277C

5
6
Ori ginal COD Found COD The a vera ge
7 -1 RSD Added COD -1 RSD
Wa ter sample (mg O2 L , (mg O2 L , recovery
8 (%, n=3) (mg O2 L-1) (%, n=3)
n=3, P=0.95) n=3, P=0.95) (%)
9
10 2.00 a 5.02±0.11 0.88 97.5
11
b
12 Tap wa ter 1 3.07±0.10 1.4 2.00 4.95±0.29 2.4 94.0
13

Analytical Methods Accepted Manuscript

a
10.00 12.78±0.24 0.75 97.1
Published on 04 April 2016. Downloaded by University of California - San Diego on 05/04/2016 03:49:24.

14
15 2.00 a 4.98±0.10 0.80 99.0
16 Tap wa ter 2 3.00±0.12 1.7 c
17 2.00 4.99±0.13 1.0 99.5
a
18 Bottled wa ter 1 0.28±0.02 3.4 1.00 1.26±0.01 0.34 98.0
19 b
1.50 1.84±0.10 2.1 94.7
20 Bottled wa ter 2 0.42±0.04 3.5 c
21 1.50 1.90±0.06 1.3 98.7
22 a
Bottled wa ter 3 0.55±0.05 3.3 10.00 10.62±0.15 0.58 100.7
23
24 The supers cript (a, b and c) represents the addi tional subs tances of KHP, phenol and glucose, and thei r theoretical COD value were the
-1 -1
25 equi valent of 1.175, 2.380 and 1.066 mg O 2 L per mass content uni ts of 1.00 mg L , respecti vel y.
26
27 anal yzi ng sa mpl es containi ng COD l oa ds as l ow as 0. 30 mg O 2 methods for the exami nation of water and waste wate r,
28 L-1 . America n Public Health Ass ociati on, America n Water Works
29 Associati on and the Water Environment Federa tion,
30 Was hington DC., 1999.
31 Conclusions 2 Standards for drinking water quality, The Sta te
32 Envi ronmental Protecti on Administration of China,
33 In s ummary, by means of the novel di ges tion mode empl oyed
Nati onal Sta ndard GB 5749, Chi na, 2006.
34 two oxi da nts, KMnO4 a nd K2 Cr2O 7, the proposed method has
3 Water quality-de termination of Pe rmanganate inde x, The
35 provi ded a credi bl e a nal yti cal approach for th e a ccurate
State Environmental Protecti on Admi nistrati on of Chi na,
36 determi nati on of l ow-l evel COD val ues in dri nki ng wa ter
Nati onal Sta ndard GB 11892-89, Chi na, 1990.
37 sa mpl es. Under the opti mized operati on conditi ons, i n the
4 Water quality-determi nati on of the che mical oxyge n
38 case of sa mpling vol ume of 10.0 mL, the detection li mi t of 0.12
demand-dichromate method, The State Environmental
39 mg O2 L -1 a nd a linear ra nge of 0.2-25.0 mg O2 L -1 ha ve been
Protection Administrati on of Chi na, Nati onal Standard GB
40 achieved. This method not only exhi bits a rel ati ve mea n error
11914-89, China , 1990.
41 of onl y 1.08% for a KHP sta nda rd sa mpl e a t the COD level of
5 E. Amana tidou, E. Tri koili dou, G. Sa mi otis, N. P. Benetis and
42 0.50 mg O2 L -1, but als o poss esses ma ny a dvanta ges of
N. Ta ousani dis, Anal. Me thods, 2012, 4, 4204-4212.
43 automati c potenti ometri c titrati on mode, good reproduci bility
6 J. Hejzlar a nd J. Kopá ček, Analyst, 1990, 115, 1463-1467.
44 and less consumed chemi cals. Moreover, the method has been
7 J. Akhoundzadeh, M. Costas, I. La villa, M. Cha msaz and C.
45 successf ull y a pplied to determi ne l ow-level COD val ues i n real
Bendi cho, Microchi m. Acta, 2013, 180, 1029-1036.
46 dri nki ng sa mpl es with the satisf actory accura cy a nd precisi on.
8 C. E. Domi ni, M. Hi dal go, F. Ma rken a nd A. Ca nals, Anal. Chi m.
47 For the sa me reas ons, this method ma y al so hopefull y become
Acta, 2006, 561, 210-217.
48 as a sta nda rd method f or the COD determinati on of vari ous
9 M. D. Da ttatray, P. V. Atul and M. B. Nivedita, Environ. Sci.
49 envi ronment water bodi es.
50 Technol., 2005, 39(16), 6198-6201.
51 10 A. Ca nals and M. R. Hernández, Anal. Bioanal. Che m., 2002,
52 Acknowledgements 374, 1132-1140.
53 11 S. Q. Zha ng, L. H. Li a nd H. J. Zha o, Envi ron. Sci. Technol.,
54 The authors gratef ully a cknowl edge the Na ti onal Science 2009, 43(20), 7810- 7815.
55 Founda ti on of China (No. 21167015 , 21174114) for fi na ncial 12 Z. Y. Zha ng, X. Chang a nd A. C. Chen, Sens. Actuators, B, 2016,
56 support. 223, 664- 670.
57 13 S. J. Yuan, R. Y. Mao, Y. G. Li, Q. H. Zhang a nd H. Z. Wa ng,
58 Electrochi m. Acta, 2012, 60, 347-353.
59 Notes and references 14 L. H. Zhu, Y. E. Chen, Y. H. Wu, X. R. Li and H. Q. Ta ng, Anal.
60 Chi m. Acta, 2006, 571, 242-247.
1 L. S. Clesceri, A. E. Greenberg a nd A. D. Eaton, Standard

This journal is © The Royal Society of Chemistry 20xx Anal . Method s, 2016 , 00, 1-3 | 7

Please do not adjust margins

 Please do not adjust margins
Analytical Methods Page 8 of 9

1 Analytical Methods ARTICLE

2
3 15 C. F. Li and G. W. Song, Sens. Actuators, B, 2009, 137, C. H. Connell, Anal. Chem., 1958, 30(9), 1482-1485. View Article Online
4 432-436. 29 S. K. Bharga va, J. Tardi o, J. Prasa d, K.DOI: 10.1039/C6AY00277C
Föger, D. B. Akoleka r
5 16 T. Kondo, Y. Ta mura, M. Hos hi no, T. Wata na be, T. Ai ka wa, M. and S. C. Grocott, Ind. Eng. Che m. Re s., 2006, 45(4),
6 Yuasa and Y. Ei na ga, Anal. Che m., 2014, 86, 8066-8072. 1221-1258.
7 17 J. Q. Wang, C. Wu, K. B. Wu, Q. Cheng a nd Y. K. Zhou, Anal. 30 E. Saputra, S. Muha mma d, H. Q. Sun, H. M. Ang, M. O. Ta dé
8 Chi m. Acta, 2012, 736, 55-61. and S. B. Wa ng, Appl. Catal., B, 2013, 142-143, 729- 735.
9 18 J. Q. Yang, J. W. Chen, Y. K. Zhou and K. B. Wu, Se ns. 31 J. G. Fu, Z. X. He, H. Wang, W. Lia ng and C. Guo, Min. Sci.
10 Actuators, B, 2011, 153, 78-82. Technol., 2010, 20(6), 0877-0881.
11 19 J. Q. Wa ng, N. Ya o, M. Li, J. Hu, J. W. Chen, Q. L. Ha o, K. B. 32 C. E. Domi ni, L. Vidal and A. Ca nals, Ultrason. Sonochem.,
12 Wu and Y. K. Zhou, Microchi m. Acta, 2015, 182, 515–522. 2009, 16, 686- 691.
13

Analytical Methods Accepted Manuscript

20 C. Wa ng, J. C. Wu, P. F. Wang, Y. H. Ao, J . Hou a nd J. Qia n, 33 J. Ebina, T. Tsuts ui and T. Shirai, Water Re s., 1983, 17(12),
Published on 04 April 2016. Downloaded by University of California - San Diego on 05/04/2016 03:49:24.

14 Anal. Chi m. Acta, 2013, 767, 141-147. 1721-1726.

15 21 B. X. Li, Z. J. Zha ng, J. Wa ng, C. L. Xu, Talanta, 2003, 61, 34 O. S. Furman, A. L. Teel, M. Ahma d, M. C. Merker a nd R. J.
16 651-658. Watts, J. Environ. Eng., 2011, 137, 241-247.
17 22 W. Li u, Z. J. Zha ng and Y. Y. Zha ng, Microchi m. Acta, 2008, 35 K. C. Huang, R. A. Couttenye and G. E. Hoa g, Che mosphe re,
18 160, 141- 146. 2002, 49, 413- 420.
19 23 C. A. Al mei da, M. Savi o, P. Gonzál ez, L. D. Marti nez and R. A. 36 P. Neta, V. Madha van, H. Zemel and R. W. Fessenden, J. Am.
20 Gil, Mi croche m. J., 2013, 106, 351-356. Che m. Soc., 1977, 99, 163-164.
21
24 D. Z. Da n, R. C. Sa ndf ord a nd P. J. Worsf old, Anal yst, 2005, 37 D. D. Tang, G. K. Zhang and S. Guo, J. Colloid Inte rface Sci.,
22
130, 227- 232. 2015, 454, 44- 51.
23
25 Y. T. Hu, Y. Z. Wen a nd X. P. Wa ng, Se ns. Actuators, B, 2016, 38 W. A. Moore, F. J. Ludza ck a nd C. C. Ruchhoft, Anal. Chem.,
24
227, 393- 398. 1951, 23(9), 1297-1300.
25
26 I. Vyrides and D. C. Stuckey, Bi ore sour. Technol., 2009, 100, 39 D. Ballinger, A. Lloyd and A. Morrish, Analyst, 1982, 107,
26
979-982. 1047-1053.
27
28 27 S. J. Edwards and M. Allen, Analyst, 1984, 109, 671-672. 40 D. L. Rocha and F. R. P. Rocha, Microche m. J., 2013, 108,
29 28 F. W. Bertra m, O. T. Ca rlisle, J. E. Murra y, G. W. Wa rren and 193-197.
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60

This journal is © The Royal Society of Chemistry 20xx Anal . Method s, 2016 , 00, 1-3 | 8

Please do not adjust margins

 Page 9 of 9 Analytical Methods
View Article Online
DOI: 10.1039/C6AY00277C

1
2
3 Graphic Abstract
4
5
6
7
8
9
Published on 04 April 2016. Downloaded by University of California - San Diego on 05/04/2016 03:49:24.

10
11

Analytical Methods Accepted Manuscript

12
13
14
15
16 Develop a multistep wet-chemical oxidation digestion technique for determination of low-level COD in
17
18 drinking water by using potentiometric titration method.
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60