[Header] Format=SMU ver=3 appl=GUMWB32 MR=0 SUR=0 SUP=0 UIP=1 UCR=0 status=2 FUEB=0 [Title] Title='An acid/base titration' Ref='' Date='08/29/2007' Version='' Author='' Description=8 Description[0]='This is the example A3 of the EURACHEM /' Description[1]='CITAC Guide "Quantifying Uncertainty in Analytical Measurement", Second' Description[2]='Edition.' Description[3]='' Description[4]='A' Description[5]='solution of hydrochloric acid (HCl) is standardised against a' Description[6]='solution of sodium hydroxide (NaOH) with known content. The standardisation of' Description[7]='the NaOH solution is similar to example A2.' PictureCount=1 DCount=1 [Model] Model=19 Model[0]='{calculation of the uncertainty of V_T2}' Model[1]='' Model[2]='V_T2 = V_T2\sp\nominal * f_VT2\minus\calibration * f_VT2\minus\temperature;' Model[3]='' Model[4]='{calculation of the uncertainty of V_T1}' Model[5]='' Model[6]='V_T1 = V_T1\sp\nominal * f_VT1\minus\calibration * f_VT1\minus\temperature;' Model[7]='' Model[8]='{calculation of the uncertainty of V_HCl}' Model[9]='' Model[10]='V_HCl = V_HCl\sp\nominal * f_VHCl\minus\calibration * f_VHCl\minus\temperature;' Model[11]='' Model[12]='{molar mass of KHP}' Model[13]='' Model[14]='M_KHP = 8 * M_C + 5 * M_H + 4 * M_O + M_K;' Model[15]='' Model[16]='{calculation of the the HCl concentration}' Model[17]='' Model[18]='c_HCl = ( k_mL * m_KHP * P_KHP * V_T2) / (V_T1 * M_KHP * V_HCl ) * f_repeatability;' CE=1 CTC=1 [Components] CompOrder=3 Comp=22 Comp[0]=V_T2_ Comp[1]=V_T2\sp\nominal_ Comp[2]=f_VT2\minus\calibration_ Comp[3]=f_VT2\minus\temperature_ Comp[4]=V_T1_ Comp[5]=V_T1\sp\nominal_ Comp[6]=f_VT1\minus\calibration_ Comp[7]=f_VT1\minus\temperature_ Comp[8]=V_HCl_ Comp[9]=V_HCl\sp\nominal_ Comp[10]=f_VHCl\minus\calibration_ Comp[11]=f_VHCl\minus\temperature_ Comp[12]=M_KHP_ Comp[13]=M_C_ Comp[14]=M_H_ Comp[15]=M_O_ Comp[16]=M_K_ Comp[17]=c_HCl_ Comp[18]=k_mL_ Comp[19]=m_KHP_ Comp[20]=P_KHP_ Comp[21]=f_repeatability_ [COMP 0] Type=Temp Definition='Volume of NaOH for HCl titration' Unit='mL' Description=0 Fcov=2 NomUnit= UncUnit= CovID=1 UncID=0 Vnom=14.89 Ustd=0.0142178298597219 Neff=10000 HB=0 HC=0 HR=0 IO=0 PictureCount=1 DCount=1 [COMP 1] Type=Const Definition='Nominal volume of NaOH for HCl titration' Unit='mL' Description=11 Description[0]='The nominal volume is not associated with any uncertainties. The uncertainty of' Description[1]='the real volume of the burette has three components, repeatability, calibration' Description[2]='and temperature. The latter two are included in the uncertainty budget as' Description[3]='separate factors. Repeatability of the volume delivery is taken into account' Description[4]='via the combined repeatability term for the experiment, f_repeatability_.' Description[5]='Another factor influencing the result of the titration, which can also be' Description[6]='attributed to the automatic titration system, of which the burette is one part,' Description[7]='is the bias of the end-point detection. The titration is performed under a' Description[8]='protective atmosphere (Ar) to prevent absorption of CO_2_, which would bias the' Description[9]='titration. No further uncertainty contributions are introduced to cover the' Description[10]='bias of the end-point detection.' Vnom=14,89 PictureCount=1 DCount=1 [COMP 2] Type=TypBTriangl Definition='Uncertainty contribution to V_T2 due to instrument calibration' Unit='' Description=11 Description[0]='The limits of accuracy for a' Description[1]='20 mL piston burette are indicated by the manufacturer as typically ±0.03 ml.' Description[2]='No further statement is made about the level of confidence or the underlying' Description[3]='distribution. An assumption is necessary to work with this uncertainty' Description[4]='statement. In this case a' Description[5]='triangular distribution is assumed. Since f_VT2\minus\calibration is a' Description[6]='multiplicative factor to the nominal volume, which is only used to introduce' Description[7]='the calibration uncertainty, it has the value 1. The halfwidth of limits' Description[8]='corresponds to the relative uncertainty as stated by the manufacturer (i.e.' Description[9]='0.03 mL /' Description[10]='14.89 mL).' Vnom=1 Hlim==0.03/14.89 PictureCount=1 DCount=1 [COMP 3] Type=TypBRectang Definition='Uncertainty contribution to V_T2 due to temperature variation' Unit='' Description=12 Description[0]='The laboratory temperature can vary by ±4°C. The uncertainty of the volume due' Description[1]='to temperature variations can be calculated from the estimate of the possible' Description[2]='temperature range and the coefficient of the volume expansion. The volume' Description[3]='expansion of the liquid is considerably larger than that of the burette, so' Description[4]='only the volume expansion of the liquid is considered. The coefficient of' Description[5]='volume expansion for water is 2.1\cdot\10^-4^°C^-1^. This leads to a' Description[6]='possible volume variation of ±(15 \cdot\ 4 \cdot\ 2.1\cdot\10^-4^) mL. A' Description[7]='rectangular distribution is assumed for the temperature variation Since' Description[8]='f_VT2\minus\temperature is a' Description[9]='multiplicative factor to the nominal volume, which is only used to introduce' Description[10]='the temperature uncertainty, it has the value 1. Its uncertainty is calculated' Description[11]='as the possible volume variation divided by the volume dispensed.' Vnom=1 Hlim==2.1e-4*4 PictureCount=1 DCount=1 [COMP 4] Type=Temp Definition='Volume of NaOH for KHP titration' Unit='mL' Description=0 Fcov=2 NomUnit= UncUnit= CovID=1 UncID=0 Vnom=18.64 Ustd=0.0152223567794215 Neff=10000 HB=0 HC=0 HR=0 IO=0 PictureCount=1 DCount=1 [COMP 5] Type=Const Definition='Nominal volume of NaOH for KHP titration' Unit='mL' Description=11 Description[0]='The nominal volume is not associated with any uncertainties. The uncertainty of' Description[1]='the real volume of the burette has three components, repeatability, calibration' Description[2]='and temperature. The latter two are included in the uncertainty budget as' Description[3]='separate factors. Repeatability of the volume delivery is taken into account' Description[4]='via the combined repeatability term for the experiment, f_repeatability_.' Description[5]='Another factor influencing the result of the titration, which can also be' Description[6]='attributed to the automatic titration system, of which the burette is one part,' Description[7]='is the bias of the end-point detection. The titration is performed under a' Description[8]='protective atmosphere (Ar) to prevent absorption of CO_2_, which would bias the' Description[9]='titration. No further uncertainty contributions are introduced to cover the' Description[10]='bias of the end-point detection.' Vnom=18,64 PictureCount=1 DCount=1 [COMP 6] Type=TypBTriangl Definition='Uncertainty contribution to V_T1 due to instrument calibration' Unit='' Description=11 Description[0]='The limits of accuracy for a' Description[1]='20 mL piston burette are indicated by the manufacturer as typically ±0.03 ml.' Description[2]='No further statement is made about the level of confidence or the underlying' Description[3]='distribution. An assumption is necessary to work with this uncertainty' Description[4]='statement. In this case a' Description[5]='triangular distribution is assumed. Since f_VT1\minus\calibration is a' Description[6]='multiplicative factor to the nominal volume, which is only used to introduce' Description[7]='the calibration uncertainty, it has the value 1. The halfwidth of limits' Description[8]='corresponds to the relative uncertainty as stated by the manufacturer (i.e.' Description[9]='0.03 mL /' Description[10]='18.64 mL).' Vnom=1 Hlim==0.03/18.64 PictureCount=1 DCount=1 [COMP 7] Type=TypBRectang Definition='Uncertainty contribution to V_T1 due to temperature variation' Unit='' Description=12 Description[0]='The laboratory temperature can vary by ±4°C. The uncertainty of the volume due' Description[1]='to temperature variations can be calculated from the estimate of the possible' Description[2]='temperature range and the coefficient of the volume expansion. The volume' Description[3]='expansion of the liquid is considerably larger than that of the burette, so' Description[4]='only the volume expansion of the liquid is considered. The coefficient of' Description[5]='volume expansion for water is 2.1\cdot\10^-4^°C^-1^. This leads to a' Description[6]='possible volume variation of ±(19 \cdot\ 4 \cdot\ 2.1\cdot\10^-4^) mL. A' Description[7]='rectangular distribution is assumed for the temperature variation Since' Description[8]='f_VT1\minus\temperature is a' Description[9]='multiplicative factor to the nominal volume, which is only used to introduce' Description[10]='the temperature uncertainty, it has the value 1. Its uncertainty is calculated' Description[11]='as the possible volume variation divided by the volume dispensed.' Vnom=1 Hlim==2.1e-4*4 PictureCount=1 DCount=1 [COMP 8] Type=Temp Definition='HCl aliquot for NaOH titration' Unit='mL' Description=0 Fcov=2 NomUnit= UncUnit= CovID=1 UncID=0 Vnom=15 Ustd=0.0109355688771397 Neff=10000 HB=0 HC=0 HR=0 IO=0 PictureCount=1 DCount=1 [COMP 9] Type=Const Definition='Nominal volume of HCl for NaOH titration' Unit='mL' Description=5 Description[0]='The nominal volume is not associated with any uncertainties. The uncertainty of' Description[1]='the real volume of the pipette has three components, repeatability, calibration' Description[2]='and temperature. The latter two are included in the uncertainty budget as' Description[3]='separate factors. Repeatability of the volume delivery is taken into account' Description[4]='via the combined repeatability term for the experiment, f_repeatability_.' Vnom=15 PictureCount=1 DCount=1 [COMP 10] Type=TypBTriangl Definition='Uncertainty contribution to V_HCl due to pipette calibration' Unit='' Description=10 Description[0]='The uncertainty stated by the manufacturer for a' Description[1]='15 mL pipette is ±0.02 mL. No further statement is made about the level of' Description[2]='confidence or the underlying distribution. An assumption is necessary to work' Description[3]='with this uncertainty statement. In this case a' Description[4]='triangular distribution is assumed. Since f_VHCl\minus\calibration is a' Description[5]='multiplicative factor to the nominal volume, which is only used to introduce' Description[6]='the calibration uncertainty, it has the value 1. The halfwidth of limits' Description[7]='corresponds to the relative uncertainty as stated by the manufacturer (i.e.' Description[8]='0.02 mL /' Description[9]='15 mL).' Vnom=1 Hlim==0.02/15 PictureCount=1 DCount=1 [COMP 11] Type=TypBRectang Definition='Uncertainty contribution to V_HCl due to temperature variation' Unit='' Description=12 Description[0]='The laboratory temperature can vary by ±4°C. The uncertainty of the volume due' Description[1]='to temperature variations can be calculated from the estimate of the possible' Description[2]='temperature range and the coefficient of the volume expansion. The volume' Description[3]='expansion of the liquid is considerably larger than that of the pipette, so' Description[4]='only the volume expansion of the liquid is considered. The coefficient of' Description[5]='volume expansion for water is 2.1\cdot\10^-4^°C^-1^. This leads to a' Description[6]='possible volume variation of ±(15 \cdot\ 4 \cdot\ 2.1\cdot\10^-4^) mL. A' Description[7]='rectangular distribution is assumed for the temperature variation Since' Description[8]='f_VHCl\minus\temperature is a' Description[9]='multiplicative factor to the nominal volume, which is only used to introduce' Description[10]='the temperature uncertainty, it has the value 1. Its uncertainty is calculated' Description[11]='as the possible volume variation divided by the volume dispensed.' Vnom=1 Hlim==2.1e-4*4 PictureCount=1 DCount=1 [COMP 12] Type=Temp Definition='Molar mass of KHP' Unit='g/mol' Description=0 Fcov=2 NomUnit= UncUnit= CovID=1 UncID=0 Vnom=204.2212 Ustd=0.00376530211271287 Neff=10000 HB=0 HC=0 HR=0 IO=0 PictureCount=1 DCount=1 [COMP 13] Type=TypBRectang Definition='Atomic weight of carbon' Unit='g/mol' Description=3 Description[0]='The atomic weight of carbon and its uncertainty are taken from data listed in' Description[1]='the latest IUPAC table of atomic weights. The IUPAC quoted data is considered' Description[2]='to be of rectangular distribution.' Vnom=12.0107 Hlim=0.0008 PictureCount=1 DCount=1 [COMP 14] Type=TypBRectang Definition='Atomic weight of hydrogen' Unit='g/mol' Description=3 Description[0]='The atomic weight of hydrogen and its uncertainty are taken from data listed in' Description[1]='the latest IUPAC table of atomic weights. The IUPAC quoted data is considered' Description[2]='to be of rectangular distribution.' Vnom=1.00794 Hlim=0.00007 PictureCount=1 DCount=1 [COMP 15] Type=TypBRectang Definition='Atomic weight of oxygen' Unit='g/mol' Description=3 Description[0]='The atomic weight of oxigen and its uncertainty are taken from data listed in' Description[1]='the latest IUPAC table of atomic weights. The IUPAC quoted data is considered' Description[2]='to be of rectangular distribution.' Vnom=15.9994 Hlim=0.0003 PictureCount=1 DCount=1 [COMP 16] Type=TypBRectang Definition='Atomic weight of potassium' Unit='g/mol' Description=3 Description[0]='The atomic weight of potassium and its uncertainty are taken from data listed' Description[1]='in the latest IUPAC table of atomic weights. The IUPAC quoted data is' Description[2]='considered to be of rectangular distribution.' Vnom=39.0983 Hlim=0.0001 PictureCount=1 DCount=1 [COMP 17] Type=Result Definition='HCl solution concentration' Unit='mol/L' Description=0 Fcov=2 NomUnit= UncUnit= CovID=1 UncID=0 Vnom=0.101387161202274 Ustd=0.000183985427330987 Neff=536 HB=1 HC=0 HR=1 IO=0 PictureCount=1 DCount=1 [COMP 18] Type=Const Definition='Conversion factor 1000 mL = 1 L' Unit='mL/L' Description=0 Vnom=1000 PictureCount=0 DCount=0 [COMP 19] Type=TypBNormal Definition='Weight of KHP' Unit='g' Description=9 Description[0]='Repeatability of the wheighing is taken into account via the combined' Description[1]='repeatability term, f_repeatability_. Any systematic offset across the scale' Description[2]='will also cancel due to the wheighing by difference. The only contributing' Description[3]='source of uncertainty is the linearity of the balance. The calibration' Description[4]='certficate of the balance quotes ±0.15 mg for the linearity. The manufacturer' Description[5]='recommends using a' Description[6]='rectangular distribution to convert this linearity contribution into a' Description[7]='standard uncertatiny. This uncertainty is accounted for twice, once for the' Description[8]='tare and once for the gross mass.' Vnom=0,3888 Uexp==sqrt(2*sqr(0.00015/sqrt(3))) Fcov=1 PictureCount=1 DCount=1 [COMP 20] Type=TypBRectang Definition='Purity of KHP' Unit='' Description=3 Description[0]='In the supplier''s catalogue, the purity of the KHP is given as 100%±0.05%. No' Description[1]='further information concerning the uncertainty is given. Therefore this value' Description[2]='is assumed to be of rectangular distribution.' Vnom=1 Hlim=0,05% PictureCount=1 DCount=1 [COMP 21] Type=TypBNormal Definition='Uncertainty contribution attributed to repeatability' Unit='' Description=9 Description[0]='All uncertainty contributions due to repeatability of one of the operations are' Description[1]='combined in this factor. It includes at least the repeatability of the' Description[2]='wheighings and of the volumes delivered by the burette and the pipette. The' Description[3]='magnitude of this uncertainty contribution is assessed during the method' Description[4]='validation stage. The data shows that the overall repeatability of the' Description[5]='titration experiment is 0.1%. Since f_repeatability is a' Description[6]='multiplicative factor to the result, which is only used to introduce the' Description[7]='repeatability uncertainty, it has the value 1' Description[8]='with an uncertainty of 0.1%.' Vnom=1 Uexp=0,1% Fcov=1 PictureCount=1 DCount=1 [Correlations] Description=0 [CalCorr] CNT=25 R[0,17]=0.5261846 R[4,17]=-0.450024 R[8,17]=-0.4017443 R[12,17]=-0.0101601 R[0,2]=0.8614148 R[0,3]=0.5079021 R[4,6]=0.8045698 R[4,7]=0.5938581 R[8,10]=0.746643 R[8,11]=0.665225 R[12,13]=0.98134 R[12,15]=0.1840013 R[12,14]=0.053667 R[12,16]=0.0153334 R[17,21]=0.5510608 R[17,2]=0.4532632 R[17,6]=-0.3620758 R[17,10]=-0.2999596 R[17,7]=-0.2672504 R[17,11]=-0.2672504 R[17,3]=0.2672503 R[17,19]=0.1735877 R[17,20]=0.1590776 R[17,13]=-0.0099705 R[17,15]=-0.0018695